WO2025021962A1 - Hydrocarbon reactor with constricted neck portion and spray nozzle - Google Patents
Hydrocarbon reactor with constricted neck portion and spray nozzle Download PDFInfo
- Publication number
- WO2025021962A1 WO2025021962A1 PCT/EP2024/071219 EP2024071219W WO2025021962A1 WO 2025021962 A1 WO2025021962 A1 WO 2025021962A1 EP 2024071219 W EP2024071219 W EP 2024071219W WO 2025021962 A1 WO2025021962 A1 WO 2025021962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- feed
- reactor system
- spray nozzle
- central axis
- Prior art date
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 143
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 142
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 112
- 239000007921 spray Substances 0.000 title claims abstract description 109
- 239000012530 fluid Substances 0.000 claims abstract description 80
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 49
- 239000000376 reactant Substances 0.000 claims abstract description 35
- 238000004891 communication Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 96
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 27
- 150000001336 alkenes Chemical class 0.000 description 26
- 238000005192 partition Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- 239000002737 fuel gas Substances 0.000 description 24
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 238000002485 combustion reaction Methods 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000000446 fuel Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000010779 crude oil Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000005336 cracking Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000001273 butane Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229920002857 polybutadiene Polymers 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 naphtha Chemical class 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- DRHKJLXJIQTDTD-OAHLLOKOSA-N Tamsulosine Chemical compound CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 DRHKJLXJIQTDTD-OAHLLOKOSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003498 natural gas condensate Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/002—Cooling of cracked gases
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
- C10G9/38—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours produced by partial combustion of the material to be cracked or by combustion of another hydrocarbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Definitions
- the present disclosure is directed to reactor systems for the production of high value chemical products from liquid hydrocarbons.
- Oxidative coupling of methane converts methane into ethylene and other hydrocarbons using catalysts at moderate temperatures and pressures. This process is an alternative to traditional methods due to its potential for higher efficiency and lower environmental impact. Advances in catalyst development and reactor design can further enhance the effectiveness and selectivity of these reactions.
- Pyrolysis reactors are specialized devices used to thermally decompose organic materials in the absence of oxygen. This process, known as pyrolysis, breaks down complex molecules into simpler compounds, producing valuable products like bio-oil, syngas, and char.
- Common types of pyrolysis reactors include rotary kilns, fluidized beds, fixed beds, and tubular reactors, each suited for different applications and feedstocks. These reactors are widely used in waste management, biofuel production, and the synthesis of carbon materials.
- Hydrocarbon reactors for partial oxidation are used to convert hydrocarbon feedstocks into syngas, a mixture of hydrogen and carbon monoxide. This process involves reacting the hydrocarbons with a sub-stoichiometric amount of oxygen, meaning less oxygen than required for complete combustion.
- POX partial oxidation
- thermal partial oxidation (TPOX) is one type of partial oxidation, which operates at higher temperatures and is suitable for high sulfur feedstocks.
- Catalytic partial oxidation (CPOX) is another type of partial oxidation, which uses a catalyst to lower the reaction temperature and is ideal for low sulfur feedstocks.
- Steam crackers are reactors used to break long-chain hydrocarbons and modify smaller alkanes (i.e., naphtha, butane, ethane) into smaller molecules and olefins, such as ethylene and propylene.
- alkanes i.e., naphtha, butane, ethane
- olefins such as ethylene and propylene.
- heavy gases such as naphtha, liquefied petroleum gas (LPG), propane, butane, and ethane are fed into a furnace with steam and converted into smaller olefins.
- Steam is added to the process to increase the selectivity to olefins with reasonable conversion.
- Steam crackers operate at high temperatures (i.e., from 750 °C to 900 °C) and have residence times of around 100 to 500 milliseconds.
- Steam crackers can suffer from heat losses and complexity associated with separate exothermic (combustion in the furnace) and endothermic steps (cracking in the process tubes). The presence of inert compounds in the combustion and process side also affects the overall efficiency. Metallurgical limitations of the reactors also limit the temperatures that can be used. Ideally, higher temperatures with shorter contact times result in better selectivity and conversion to smaller olefins. Steam crackers can also experience plugging from coking, which can increase the capital cost and operational expenses and this also prevents cracking certain heavier feeds. Because commercial crackers are typically optimized for only a certain type of feedstock, feedstock flexibility may also be limited. Typically, these crackers also operate at process pressures less than 200 kPa and that increases the capital cost of the downstream operations.
- the reactor system includes a feed assembly including a feed assembly wall that defines a central chamber. A central axis of the reactor system passes through the feed assembly.
- the feed assembly includes multiple flow passages oriented with respect to the central axis. Each flow passage is configured to introduce a gas feed into the central chamber in a swirling flow pattern.
- the reactor system includes an inlet assembly that includes a circumferential wall that defines a smoothly-curved converging-diverging conduit.
- the central axis passes through the inlet assembly.
- the circumferential wall converges towards the central axis and then diverges away from the central axis to define the smoothly-curved converging-diverging conduit.
- the circumferential wall joins the feed assembly wall to place the smoothly-curved converging-diverging conduit in fluid communication with the central chamber of the feed assembly.
- the reactor system includes a spray nozzle positioned relative to the central chamber and configured to introduce a hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit in a pattern nonperpendicular to the central axis.
- the reactor system includes a reactor vessel that includes a reactor wall that defines a reaction chamber and an outlet. The central axis of the reactor system passes through the reactor vessel.
- the reactor wall joins the circumferential wall of the feed assembly to join the smoothly-curved converging-diverging conduit in fluid communication with the reactor chamber of the reactor vessel.
- the smoothly-curved converging-diverging conduit includes a geometry that facilitates recirculation and backflow of fluids within the reactor vessel.
- the gas feed and the hydrocarbon reactant feed react in the reactor vessel to convert the hydrocarbon reactant feed into a converted hydrocarbon product.
- the outlet is configured to flow the converted hydrocarbon product out of the reactor chamber.
- a feed inlet is formed as a length of conduit that joins the feed assembly wall.
- the spray nozzle is positioned and oriented for introducing the hydrocarbon reactant feed into the central chamber through the feed inlet.
- the conduit includes an inlet axis that is aligned with the central axis to introduce the hydrocarbon reactant feed axially or non-perpendicularly with respect to the central axis of the central chamber.
- the feed assembly includes a manifold including the spray nozzle.
- the manifold includes multiple spray nozzles. Each spray nozzle is configured to introduce the hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit into the reactor vessel in a respective pattern non-perpendicular to the central axis.
- the spray nozzle is configured to introduce the hydrocarbon reactant feed in a non-swirling pattern.
- the spray nozzle is configured to introduce the hydrocarbon reactant feed in a liquid spray flow pattern that is non-parallel to the central axis.
- the spray nozzle is configured to introduce the hydrocarbon reactant feed at a spray angle relative to the central axis.
- the spray nozzle is configured to introduce the hydrocarbon reactant feed with a Sauter Mean Diameter (SMD) of droplets from 1 pm to 250 pm.
- SMD Sauter Mean Diameter
- An aspect combinable with any other aspect includes the following features.
- the spray nozzle is oriented with respect to the central axis to avoid the liquid feed from being forced by centrifugal forces against the reactor wall.
- the spray nozzle is configured to form droplets with a Dvo.s from 10 microns to 50 microns.
- the spray nozzle is configured to allow the introduction of two fluids.
- a first of the two fluids is a liquid phase fluid.
- a second of the two fluids is a gas phase fluid.
- the spray nozzle is a two-fluid spray nozzle.
- the two- fluid spray nozzle includes a mixing chamber to mix the two different fluids prior to being discharged as a spray.
- the spray nozzle is not a two-fluid spray nozzle.
- An aspect combinable with any other aspect includes the following features.
- the two different fluids are mixed and combined upstream of the spray nozzle.
- the first of the two fluids is the hydrocarbon reactant feed.
- the second of the two fluids is a gaseous hydrocarbon or steam.
- Each flow passage includes a respective inlet oriented to impart the swirling flow pattern to the respective gas feed.
- Each flow passage includes one or more guide vanes oriented to impart the swirling flow pattern to the respective gas feed.
- An aspect combinable with any other aspect includes the following features.
- the diverging portion of the converging-diverging conduit has an overall angle of divergence from 25° to 55° relative to the central axis.
- An aspect combinable with any other aspect includes the following features.
- the converging-diverging conduit has a circular cross-section with respect to the central axis.
- FIG. 1 is an elevational, cross-sectional view of a reactor system for the conversion of liquid plastic-waste-derived pyrolysis oils, waxes, and oligomers in accordance with various embodiments of the disclosure;
- FIG. 2 is a perspective view of a feed assembly of the reactor system of FIG. 1 in accordance with various embodiments of the disclosure
- FIG. 3 is cross-sectional perspective view of the feed assembly and upstream end of a reaction chamber of the reactor system of FIG. 1;
- FIG. 4 is a plot of the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in a reactor systems, such as that of FIG. 1;
- FIG. 5 is a plot showing the Computational Fluid Dynamics (CFD) calculations of spray evaporation in a reactor, such as that of FIG. 1, wherein all the liquid was vaporized within 5 mm from the injection point; and
- CFD Computational Fluid Dynamics
- FIG. 6 is a plot of the results of testing of a FLOWMAX® FM3A two-fluid nozzle using liquid water and air showing the various droplet sizes under various flow conditions.
- FIG. 7 is a plot of selectivity in weight percent of light olefins and aromatics for the conversion of a 20 wt% liquid crude feed and wide range naphtha in an ANJEVOC reactor;
- FIG. 8 is a plot of the conversion percentage and bulk gas temperature for the conversion of a 20 wt% liquid crude feed and wide range naphtha in the ANJEVOC reactor;
- FIG. 9 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Khuff gas condensate (KGC) crude oil with butane in the ANJEVOC reactor.
- KGC Khuff gas condensate
- FIG. 10 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Arab extra light (AXL) crude oil with butane in the ANJEVOC reactor.
- FIG. 11 shows selectivity in weight percent of light olefins and aromatics for either full range pyoil or polybutadiene oligomer with ethane in the ANJEVOC reactor.
- unique reactor technology is described utilized to convert a hydrocarbon product into a converted hydrocarbon product that is or includes high value chemicals, such as light olefins and aromatics.
- the conversion of these materials may be accomplished in single step of processing or with reduced or minimal processing steps and equipment, as compared to conventional steam cracking processing systems. More specifically, the conversion may be achieved by utilizing ANJEVOC (ANnular JEt VOrtex Chamber) reactor technology that produces annular highly swirled jets of feed gases where hydrogen (or other fuels such as natural gas, recycled syngas, etc.) and oxygen gases are mainly used to generate the heat required for cracking of hydrocarbons.
- ANJEVOC ANnular JEt VOrtex Chamber
- Examples of such ANJEVOC reactors are described in U.S. Patent Nos. 11,020,719 and 11,123,705; and International Publication Nos. W02022/010821A1; W02022/010822A1, and
- the central location of the nozzle injects the liquid hydrocarbon reactant feed into an area of a reactor with a low swirl velocity (e.g., swirl velocity of less than 5 m/s).
- the location along with the droplet size allows the liquid droplets to vaporize before the droplets enter an area of the feed assembly with higher swirl velocities, thereby preventing rapid coking of the reactor.
- the combination of a location for the nozzle and a droplet size generated by the nozzle thus provides certain unique advantages.
- X, Y, and/or Z can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ).
- “at least one of X, Y, and Z” can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ)
- wt% or “mol%” refer to a weight or molar percentage of a component, respectively, based on the total weight or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol% of component.
- FIG. 1 an elevational cross-sectional representation of a reactor system 10 for the conversion of liquid hydrocarbons is shown.
- the reactor system 10 is configured for the conversion of liquid hydrocarbons in the form of pyoil and waxes and/or oligomers, which may be produced from the pyrolysis of plastic waste, such as MPW, or from other sources.
- the reactor system 10 can also be used to convert gaseous hydrocarbons in conjunction with the liquid hydrocarbons.
- the reactor system 10 may constitute an ANJEVOC reactor and includes a reactor vessel 12 having a reactor wall 14 that defines an interior reaction chamber 16.
- the reactor wall 14 may have a cylindrical configuration with a constant diameter along all or a portion of its length, which may constitute a majority (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) of its length.
- the reactor vessel 12 is oriented vertically so that the cylindrical reactor wall 14 is oriented in an upright orientation with downward flow.
- the reactor can have other orientations (e.g., horizontal, sloped, or upright with upward flow), however, because the process is controlled by the centrifugal force, which exceeds the gravitational force by several orders of magnitude.
- the reactor vessel 12 may be configured to provide a length to diameter ratio (L/D) of at least 2.
- the reactor vessel 12 may be formed from steel.
- a cooling jacket can be provided around all or portions of the reactor vessel 12, wherein a second steel wall 18 is positioned around and spaced from the inner reactor wall 14 and a cooling fluid, such as water, may be circulated through the jacket formed between the walls 14, 18.
- the reactor wall 14 may be formed from one or more layers of refractory material that line the interior of an outer steel wall to reduce heat loss and sustain the high temperatures of the reactor 10.
- the reactor wall 14 is cooled internally by the high-velocity near-wall gas flow pushed by centrifugal forces against the reactor wall 14 so that in some applications no exterior cooling jacket is required.
- This also allows refractory materials to be used for the interior of the reactor wall 14.
- Refractory materials typically cannot be used with conventional cracking reactors with pure oxygen due to the higher temperatures (e.g., from 2000 °C to 2800 °C).
- Reaction temperature for the conversion of liquid hydrocarbons, such as crude oil, in the reactor system 10 will typically range from 800 °C to 2500 °C.
- An outlet 20 is provided at a lower or downstream end of the reactor vessel 12 for removing or discharging cracked products from the reaction chamber 16.
- the outlet diameter can be same as the diameter of the reactor wall 14 or the outlet diameter may be reduced to accelerate the flow before quenching and collection downstream.
- the reactor 10 includes a reactor inlet assembly 22 that is coupled or joined to the upper or upstream end of the reactor wall 14 of the reactor vessel 12.
- the reactor vessel 12 is oriented vertically with the inlet assembly 22 located above the reactor vessel 12. This is so that any downstream liquid quenching fluids (e.g., water) that are used within the reaction chamber 16 to quench the reaction gases are carried by gravity to the outlet 20 and not towards the upstream end towards the inlet assembly 22.
- liquid quenching fluids e.g., water
- the inlet assembly 22 defines a converging-diverging conduit 24 defined by a circumferential wall 26 that surrounds a central axis 28 of the reactor 10. is the central axis 28 of the reactor 10 may be the same or coincide with the central axis of each of the inlet assembly 22 or conduit 24 and reactor vessel 12.
- the circumferential wall 26 extends from opposite upstream and downstream ends of the converging-diverging conduit 24.
- upstream and downstream or similar expressions with respect to describing various components of the reactor system 10 shall refer to the position of the component with respect to the direction of overall fluid flow through the reactor 10 along the central axis 28.
- the circumferential wall 26 smoothly tapers in width or diameter from the upstream ends to define an annular constricted neck portion located between the downstream and upstream ends of the converging-diverging conduit 24.
- the circumferential wall 26 smoothly expands or diverges in width or diameter downstream from the annular constricted neck portion.
- the interior of the circumferential wall 26 may have a circular perpendicular transverse cross section with respect to the central axis 28 along all or a portion of its length.
- the circumferential wall 26 defines an interior flow path of the feed assembly 32, with the constricted neck portion being part of the smoothly curved and streamlined converging-diverging nozzle of the inlet assembly 22.
- the nozzle geometry of the converging-diverging conduit 24 is configured based upon the theory relating to swirling conical jets of a viscous incompressible fluid. This phenomenon is described in the journal article by Pannala et al., entitled “Novel Annular Jet Vortex Reactor for High-Temperature Thermochemical Conversion of Hydrocarbons to Acetylene,” published in ACS Engineering in 2022 (Pannala, S. et al. ACS Engineering 2022, 2(5), 406-420). The downstream or diverging portion of the conduit 24 is configured for non- supersonic fluid flow.
- Conduits or nozzles configured for supersonic flow are configured differently from the conduit 24 to provide supersonic flow downstream to form a shockwave.
- the diverging conduit 24 does not form such supersonic flow or shockwave.
- the conduit 24 has a geometry that facilitates a recirculation and backflow of gases within the interior reaction chamber 16 near the central axis 28 in combination with annular swirling jet gas flow adjacent to the inner reactor wall 14.
- the conduit 24 will have a greater angle of divergence than the angle of divergence typically utilized in de Laval nozzles, which have an angle of divergence of 15° or less.
- the overall angle of divergence “A” (FIG.
- the angle of divergence A for the diverging portion of the conduit 24 discussed herein is from 25° to 55°.
- the angle of divergence A is from at least, equal to, and/or between any two of 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, 40°, 41°, 42°, 43°, 44°, 45°, 46°, 47°, 48°, 49°, 50°, 51°, 52°, 53°, 54°, and 55°.
- the large divergence angle leads to recirculation of fluid flow at the reactor wall 14, as a result of the upstream swirling flow coupled with the convergent divergent conduit 24.
- the downstream end of the diverging portion of conduit 24 joins the reactor wall 14 at an inlet of the reaction chamber 16 around its perimeter so that the conduit 24 is in fluid communication with the reaction chamber 16 of the reactor vessel 12.
- the upstream end of the converging portion of conduit 24 forms an inlet for the reactor vessel 12.
- a reactor feed assembly 32 is provided with the reactor system 10.
- a perspective view of the feed assembly 32 is shown in FIG. 2.
- the reactor feed assembly 32 joins the upstream end of conduit 24 and is in fluid communication with the conduit 24, with the central axis 28 passing through the reactor feed assembly 32.
- the feed assembly 32 includes a downstream feed assembly wall 34 that extends circumferentially around and joins the upstream end of the converging portion of conduit 24.
- the feed assembly wall 34 or circumferential portions thereof are oriented perpendicularly or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
- upstream feed assembly wall 36 Axially spaced upstream from the downstream wall 34 along the central axis 28 is an upstream feed assembly wall 36.
- the upstream wall 36 or circumferential portions thereof are oriented perpendicular to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
- An upstream gas partition wall 38 and a downstream gas partition wall 40 are axially spaced between the downstream and upstream feed assembly walls 34, 36 and are axially spaced from one another, with the upstream partition wall 38 being positioned upstream from the downstream partition wall 40.
- the partition walls 38, 40 or circumferential portions thereof are also each oriented perpendicularly to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
- Each of the partition walls 38, 40 has a central opening 42, 44, respectively, that surrounds the central axis 28 and is concentric with the convergingdiverging conduit 24.
- the inner ends of the partition walls 38, 40 defining the openings 42, 44 terminate at a position upstream of the converging-diverging conduit 24.
- the central openings 42, 44 each have a circular configuration.
- Other continuously-curved shapes for the central openings 42, 44 e.g., oval
- This shape may also correspond to the cross-sectional shape of the circumferential wall 26 of the converging-diverging conduit 24.
- the central openings 42, 44 will be circular in shape.
- the central openings 42, 44 may have a diameter or width that is the same or slightly different (smaller or larger) than the diameter or width of the constricted neck of the converging-diverging conduit 24 at its narrowest point.
- the upstream partition wall 38 defines an annular gas flow passage 46 located between the upstream feed assembly wall 36 and the upstream side of the upstream partition wall 36.
- the flow passage 46 constitutes an upstream annular hydrocarbon reactant feed inlet flow passage for introducing a gaseous hydrocarbon to be converted, e.g., into high value chemicals such as light olefins and aromatics.
- an annular gas flow passage 48 is defined by the downstream side of the downstream partition wall 40 and the downstream feed assembly wall 34.
- the flow passage 48 may constitute an annular steam or water inlet flow passage.
- An intermediate partition wall 50 is axially spaced between the downstream gas partition wall 40 and the upstream gas partition wall 38 to define downstream and upstream intermediate annular gas inlet flow passages 52, 54.
- the intermediate partition wall 50 also has a central opening 56 that surrounds the central axis 28 and is concentric with the converging-diverging conduit 24.
- the inner ends of the partition wall 50 defining the opening 56 terminate at a position upstream of the converging-diverging conduit 24.
- the central opening 56 may have a circular configuration. Other shapes for the central opening 56 (e.g., oval) may also be used provided such configuration facilitates the swirling of gases to provide the required swirling flow patterns described herein.
- the intermediate partition wall 50 is also oriented perpendicularly to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
- the annular flow passage 52 may constitute an oxygen or oxidizing gas flow passage to facilitate combustion.
- the annular flow passage 54 may constitute a fuel gas (e.g., H2, CH4, syngas or a combination of these) flow passage for introducing a fuel gas for combustion.
- the central axis 28 also coincides with and forms a central axis of the central chamber 58 and feed assembly 32.
- This configuration provides flow passages through which gas feeds to be cracked, steam, oxygen gas, and hydrogen-rich fuel for providing combustion heat can each be separately introduced and passed through the flow passages 46, 48, 52, 54, respectively, into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases.
- the feeds are introduced into the central chamber in a direction that is non-parallel to the central axis 28.
- one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 are configured to introduce the feeds into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases.
- the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) may be oriented in a direction that is non-parallel to the central axis 28.
- one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) may be oriented less than or equal to 5 degrees, less than or equal to 10 degrees, less than or equal to 20 degrees, less than or equal to 30 degrees, less than or equal to 40 degrees from a direction perpendicular the central axis 28.
- the upstream flow passage 46 can act as a gaseous hydrocarbon feed inlet flow passage.
- a fuel gas feed comprised of an hydrogen-rich gas feed i.e., H2
- an oxidizer i.e., O2
- oxygen-containing gas feed may be introduced into the other of the flow passages 52, 54.
- the fuel and oxygen gas feeds will be introduced into flow passages that are immediately adjacent to one another to facilitate rapid combustion.
- the downstream flow passage 52 may be used for delivering the oxidizer or oxygen-containing gas and the upstream flow passage 54 will be used for delivering the hydrogen-rich fuel gas.
- the steam feed may be introduced into the downstream annular steam inlet flow passage 48.
- the various feeds may be altered in sequences within the flow passages 46, 48, 52, 54.
- any of flow passages 48, 52, 54 can act as a gaseous hydrocarbon feed inlet flow passages.
- the steam feed may be combined or introduced with one or more of the other feeds. This may include combining the steam feed with the fuel-gas feed, the oxygen-containing gas feed, or the hydrocarbon gas feed.
- one or more of the flow passages 46, 48, 52, 54 may remain idle or be omitted from the feed assembly 32. If a flow passage is omitted, one of the partition walls 38, 40, 50 need not be present and the number of flow passages will be reduced. In such instances, certain feeds may be combined and introduced together, such as the steam feed previously discussed.
- the flow passages 46, 48, 52, 54 are configured so that the different feeds pass through flow passages perpendicularly or substantially perpendicularly to the central axis 28 in an inwardly swirling fluid flow pattern within said flow passages so that the feeds flow about the central axis 28 within the central chamber 58.
- the swirling fuel gas and oxidizer feeds combust within the central chamber 58.
- the walls 34, 36, 38, 40, and 50 forming the different flow passages 46, 48, 52, 54 are parallel to one another. However, in other cases, walls 34, 36, 38, 40, and 50 may be non-parallel to one another.
- the walls 34, 36, 38, 40, and 50 are axially spaced apart to provide the desired volume and flow characteristics for the gases flowing through them. This may be based upon the desired flow rates or linear velocities of each of the feed gases and their relative amounts. For instance, the relative volume of oxygen gas needed for the combustion is typically smaller than the volume of the hydrogen-rich fuel gas needed for the combustion. Therefore, the partition wall 50 may be spaced closer to the downstream partition wall 40 so that the flow passage 54 for the hydrogen fuel is larger and accommodates the greater flow of fuel gas. The particular spacing may depend on fuel gas and oxidizer combination, the desired volume for combustion, and nature of the hydrocarbon feeds.
- Annular gas manifolds 60, 62, 64, 66 are provided around the outer periphery of the flow passages 46, 48, 52, 54, respectively.
- the gas manifold 60 may be fluidly coupled to a gaseous hydrocarbon feed source.
- the manifold 62 may be fluidly coupled to a steam source.
- the manifold 64 may be fluidly coupled to an oxygen-containing-gas source, such as a pure O2 feed.
- the manifold 66 is fluidly coupled to a hydrogen-rich or fuel feed source, such as H2.
- the manifolds 60, 62, 64, 66 are provided with the reactor feed assembly 32 to facilitate introduction of feed gases into the flow passages 46, 48, 52, 54. In other embodiments, the different feed sources to each manifold may be varied.
- the gas inlets from the manifolds 60, 62, 64, 66 are oriented to generate an inwardly swirling flow of gases within central chamber 58 (e.g., oriented nearly tangentially with respect to an outer perimeter of the flow passages 46, 48, 52, 54).
- the gas inlets direct the incoming flow of gases along paths that extend inwardly from the walls of central chamber 58 but not along a radius of central chamber 58 directly toward the central axis 28 from the inlets.
- one or more inlets may be provided for each flow passage 46, 48, 52, 54.
- the walls 34, 36, 38, 40, and 50 that form the different flow passages of the feed assembly 32 prevent the gases from flowing axially along the direction of central axis 28 while they are contained within the flow passages 46, 48, 52, 54.
- the manifolds 60, 62, 64, 66 can be configured as standard manifolds (e.g., snail-like) as may be typically used in vortex devices.
- one or more or all of the flow passages 46, 48, 52, 54 may be provided with a plurality of circumferentially spaced guide vanes 68, 70, 72, 74 (e.g., 10 to 60 guide vanes for each flow passage).
- Each guide vane 68, 70, 72, 74 may be a planar member that is oriented in a plane that is parallel to the central axis 28 and extends between the walls 34, 36, 38, 40, and 50.
- the guide vanes 68, 70, 72, 74 may be circumferentially spaced an equal distance from one another.
- the guide vanes 68, 70, 72, 74 may be fixed in place, with the upper and lower side edges of the guide vanes being joined along their lengths or a portion of their lengths to the walls 34, 36, 38, 40, and 50 so that there are no air gaps between the side edges of the vanes 68, 70, 72, 74 and the walls 34, 36, 38, 40, and 50.
- the guide vanes are movable. In such cases, the upper and lower side edges of the vanes 68, 70, 72, 74 may be closely spaced from the walls 34, 36, 38, 40, and 50 to provide a small clearance to allow movement. The close spacing may minimize air gaps through which gases may pass.
- the vanes 68, 70, 72, 74 may be oriented so that the plane of the vane is in a non-parallel or slanted orientation relative to the central axis 28. In such cases, the side edges may be fixed to the walls 34, 36, 38, 40, and 50 or remain closely spaced from walls 34, 36, 38, 40, and 50 to minimize air gaps.
- the guide vanes 68, 70, 72, 74 may be configured as airfoils, such as described in U.S. Patent No. 11,123,705.
- the guide vanes 68, 70, 72, 74 are provided adjacent to the outer perimeter of the flow passages 46, 48, 52, 54 and are spaced in an annular or circular ring pattern near the manifold inlets. In other reactor systems, they may be provided in an annular pattern at other positions located radially inward or further within the interior of the flow passages 46, 48, 52, 54. Alternatively, one or more additional annular sets of guide vanes may be located radially inward from those located along the outer periphery to facilitate inwardly swirling fluid flow.
- Feed gases from the manifolds 60, 62, 64, 66 are delivered nearly tangentially to the outer perimeter of the central chamber 58, where the guide vanes 68, 70, 72, 74 may direct the gas flow in an inwardly swirling or spiraling fluid flow pattern within the central chamber 58.
- the inlets from the manifolds 60, 62, 64, 66 may be oriented or directed to impart the full inwardly swirling fluid flow without the use of or need for guide vanes.
- the guide vanes 68, 70, 72, 74 may impart the full swirling flow of the introduced gases, such as in instances where the gas from the manifold inlets may be directed radially toward the central axis 28 or do not impart the full desired swirling flow. In such cases the guide vanes 68, 70, 72, 74 prevent flow directly toward the central axis 28 and direct the flowing gases nearly tangentially with respect to the inner walls of central chamber 58 to provide the inwardly swirling or spiraling fluid flow pattern.
- the guide vanes 68, 70, 72, 74 of each flow passage 46, 48, 52, 54 may be mounted on actuators (not shown) so that they can be selectively movable to various positions to provide a selected inwardly spiraling flow pattern.
- the guide vanes 68, 70, 72, 74 may be pivotal about an axis that is parallel to the central axis 28 so that the vanes 68, 70, 72, 74 may be moved to various positions.
- the orientation of the vanes 68, 70, 72, 74 and/or the orientation of the inlets of the manifolds 60, 62, 64, 66 of each flow passage will provide swirling or spiraling fluid jet flow that is in the same rotational direction about the central axis 28, i.e., clockwise or counterclockwise.
- gases within each of the flow passages will flow clockwise or counterclockwise about the central axis 28.
- the vanes 68, 70, 72, 74 will all introduce gases at the same angle inner relative to the walls of central chamber 58 to provide the desired swirling fluid flow characteristics. If the vanes 68, 70, 72, 74 are movable, then they will typically be actuated to move in unison or close to unison.
- oxygen and hydrogen fuel gases from flow passages 52, 54, gaseous hydrocarbon feed from flow passage 46, and steam from flow passage 48 may be discharged into the central chamber 58 of the feed assembly 32. Because the oxygencontaining gas and hydrogen-rich fuel gas are introduced separately from one another and not as mixture, this eliminates safety issues that would otherwise occur if these gases were premixed prior to their introduction into the feed assembly 32. Furthermore, the combustion reaction takes place rapidly, with most of the combustion occurring within a small space within the central chamber 58 where the two streams of oxygen-containing gas and hydrogen- rich fuel gas from the flow passages 52, 54 are mixed after being discharged from the flow passages 52, 54.
- the combustible mixture can be ignited, e.g., using a spark, chemicals or pilot flame that extends through the bottom surface or side surfaces of the reactor. Suction from the swirling flow can transport heat from an ignition device to the combustion zone 58 to initiate the ignition.
- a liquid feed inlet 76 is also formed in the upstream feed assembly wall 36 for introducing, into the feed assembly 32, all or a portion of the liquid hydrocarbons to be converted by the reactor system 10 into, e.g., high value chemicals such as light olefins and aromatics. In certain embodiments, there may be more than one or multiple liquid feed inlets 76.
- the liquid feed inlet 76 may be formed as a length of conduit that joins the feed assembly wall 36.
- the conduit may include an inlet axis that is aligned with and/or parallel to the central axis 28 so that the liquid feeds or a majority (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) of the liquid feeds introduced through the inlet 76 may be introduced axially or at a non-perpendicular angle with respect to the central axis 28 into the central chamber 58. In other words, the liquid feeds introduced through the inlet 76 are not introduced perpendicularly to axis 28.
- a liquid feed manifold 80 may be used to introduce liquid feeds through the liquid feed inlet 76.
- the manifold 80 is fluidly coupled to a liquid feed source comprising the liquid hydrocarbon to be converted.
- the manifold 80 comprises one or more spray nozzles 78 that may be used to introduce the liquid feed as a liquid spray (i.e., a spray of liquid droplets) into the central chamber 58.
- the manifold 80 may comprise multiple spray nozzles 78 positioned and oriented for introducing, into the central chamber 58 through the liquid feed inlets 76, the liquid feed as multiple sprays of droplets.
- the droplets in the liquid feed define a non-swirling spray and/or a radially-extending fanned pattern so that all or a portion of the droplets are not parallel to the central axis, but will have axial and radial flow velocity components.
- the droplet pattern may be centered on or close to the central axis where the swirl velocities are lowest.
- one or more spray nozzles 78 introduce liquid into the central chamber 58 of the feed assembly 32 where the swirl velocity of the swirling fluid flow is less than 5 m/s during operation of the reactor 10.
- One or more spray nozzles may be located within a certain placement radius (“PR”) defined from a point where the central axis 28 intersects a plane defined by the upstream wall 36 of the feed assembly 32.
- PR placement radius
- the PR is no greater than 30% of the radius of the central chamber 58. In other embodiments, the PR is no greater than 20% of the radius of the central chamber 58.
- the combination of axial and radial flow velocity components define a spray pattern that has a low spray angle and keeps the pattern close to the central axis 28.
- the droplets are directed primarily axially (e.g., to define a spray angle of 40° or less).
- a spray angle helps ensure that liquid droplets are vaporized before being caught in the swirling gas flow and forced by centrifugal forces against the reactor wall, which can lead to coking.
- the spray pattern may have a spray angle of at least, equal to, and/or between any two of 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°,
- the spray pattern may be a solid conical, hollow-conical, linear stream, or flat spray pattern.
- the liquid feed inlet 76 is does not include guide vanes, such as the vanes 68, 70, 72, 74, or other structures that may impart a swirling fluid flow to the liquid hydrocarbon before it enters the central chamber 58.
- the atomized spray with liquid droplets is primarily concentrated close to the central axis 28 of the reactor 10 where the swirl velocity is lowest. In effect, the liquid droplets are concentrated at the “eye” of the swirling flow. Higher swirl velocities are encountered away from the central axis 28 or centerline and closer to the walls. These higher swirl velocities could deposit the atomized droplets on the walls and guide vanes causing coking and fouling.
- the small droplets interact with the counter current flow of the high temperature gases from the combustion and strong recirculation to vaporize the droplets and follow the other hydrocarbon gases to increase heat and crack in the reactor 10.
- the spray nozzle(s) 78 may be selected and/or configured to provide a particular droplet size.
- the spray nozzle(s) may be constructed or configured to a provide droplets under the selected flow conditions (e.g., pressure, velocity) having a Sauter Mean Diameter (SMD) or D32 from 1 pm to 250 pm.
- SMD Sauter Mean Diameter
- D32 size is defined as the ratio of droplet volume to the surface area of the droplets in a spray.
- Droplet measurements may be determined using phase doppler interferometer (PDI) techniques.
- the spray nozzle(s) at the liquid feed inlet 76 may provide a SMD size for the liquid hydrocarbon feed of from at least, equal to, and/or between any two of 1 p , 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 1
- FIG. 4 shows the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in the reactor.
- FIG. 5 shows the Computational Fluid Dynamics (CFD) calculations of spray evaporation in the reactor, wherein all the liquid was vaporized within 5 mm from the injection point.
- the plot shows the volume fraction of liquid of the spray that ranges from approximately 2.5 xlO' 5 at its introduction and goes to 0 (which indicates that all the liquid was vaporized).
- Weighted average droplet size may include a mass (volume) median or 50% diameter (Dvo.s), which is the diameter at which 50% of the total volume of droplets are contained in particles with smaller diameters.
- the Dvo.s of the droplets may be from at least, equal to, and/or between any two of 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm,
- the Dvo.i is the diameter below which 10% of the total volume of droplets are found.
- the Dvo.i of the spray may be from at least, equal to, and/or between any two of 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm,
- the spray nozzle is configured to form droplets with a Dvo.i from 5 pm to 25 pm.
- the Dvo.9 is the diameter below which 90% of the total volume of droplets are found.
- the Dvo.9 of the spray may be from at least, equal to, and/or between any two of 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm,
- the spray nozzle is configured to form droplets with a Dvo.9 from 20 pm to 100 pm.
- the liquid hydrocarbon may be modified to have a dynamic viscosity from 0.1 cP to 1000 cP prior to or at its introduction, as measured using ASTM D445, but at the temperature of operation (i.e., the temperature of the liquid hydrocarbon when passed through the nozzle(s)).
- the liquid hydrocarbon feed may in some cases be preheated to a temperature between 25 °C to 400°C and viscosity measured at this temperature.
- the droplet size is approximately proportional to dynamic viscosity to the power of 0.2 and thus lower dynamic viscosity leads to smaller droplet size.
- fluids with lower dynamic viscosity also have lower surface tension and the droplet size is approximately correlated to surface tension to the power of 0.5.
- the liquid hydrocarbon may be modified to have a dynamic viscosity from at least, equal to, and/or between any two of 0.1 cP, 0.2 cP, 0.3 cP, 0.4 cP, 0.5 cP, 0.6 cP, 0.7 cP, 0.8 cP, 0.9 cP, 1 cP, 2 cP, 3 cP, 4 cP, 5 cP, 6 cP, 7 cP, 8 cP, 9 cP, 10 cP, 15 cP, 20 cP, 30 cP, 40 cP, 50 cP, 60 cP, 70 cP, 80 cP, 90 cP, 100 cP, 150 cP, 200 cP, 250 cP, 300 cP, 350 cP, 400 cP,
- Modification of the hydrocarbon may include heating the hydrocarbon to a sufficient temperature and/or combining the liquid hydrocarbon with a solvent or low viscosity component to lower the dynamic viscosity.
- solvents may include an oligomer, wax or other liquid have a lower dynamic viscosity than the hydrocarbon being modified.
- the spray nozzle(s) 78 may be configured or selected as a two-fluid nozzle.
- Such two-fluid nozzles may allow for the introduction of two different fluids, each having different properties from the other.
- the liquids could include a liquid phase fluid and vapor phase fluid that are each sprayed simultaneously through the nozzle 78.
- the two-fluid nozzle 78 may have a mixing chamber where the two fluids are mixed prior to being discharged as a spray.
- Such two-fluid nozzles also provide internal mixing of the two fluids to prevent clogging, as well as providing a fine atomized spray having the above-stated droplet size.
- Such two-liquid spray nozzles are described, for example, in U.S. Pat.
- Two-fluid nozzles may facilitate rapidly diffusing the mixture from the outlet, promoting atomization, and forming droplets, which can be conveyed easily by the atomization gas. This can reduce liquid deposition on the mixed gas outlet and prevent clogging.
- two-fluid nozzles can help to atomize and disperse high viscosity liquids by flowing a gaseous phase with the high viscosity liquid phase.
- a suitable commercially available two-fluid nozzle for use as the spray nozzle(s) 78 may include that marketed as the FLOWMAX® X-Series or FLOWMAX® FM3A nozzle, available from Spraying Systems Co., Tokyo, Japan.
- the energy input to the spray nozzle is equal to the pressure drop across the nozzle multiplied by the flow rate.
- the choice of single-phase or two-phase nozzle depends on the pressure drop of the nozzles.
- the selection of a single-phase or two-phase nozzle also depends on various requirements (e.g., (i) spray angle, (ii) hollow vs. full spray cone, and (iii) internal mixing and external mixing to address fouling, which can be achieved using a two-phase nozzle).
- spray nozzle selection may depend on high temperature operability, coking and fouling characteristics, erosion, ability to detect and unplug the narrow openings of the nozzles, etc.
- two-fluid nozzles provide a broad range of control over the droplet size distribution and ability to self-clean as the vapor phase can be steam.
- a disadvantage may be that slight variations in vapor phase or liquid phase flow rates or pressures can dramatically vary the droplet and spray characteristics.
- the liquid hydrocarbon may be introduced into the liquid feed inlet 76 through the two-fluid spray nozzle 78 along with a gaseous hydrocarbon and/or steam (i.e., superheated steam) as the second fluid.
- the spray nozzle 78 is coupled to one end of the spray manifold 80 that is fluidly coupled to separate upstream liquid hydrocarbon and gas feed (i.e., steam and/or gaseous hydrocarbons) sources.
- the range of pressures for the liquid feed versus vapor feed depend on the design of the nozzle. For example, FIG.
- FIG. 6 shows the results of testing of a FLOWMAX® FM3 A two-fluid nozzle using liquid water and air under different flow conditions and the various droplet sizes (i.e., D32, DVO.9, Dvo.99).
- the liquid pressure was varied in the range of 1-3 barg at a constant gas pressure of 4.14 barg.
- the corresponding liquid flow was in the range of 1-11 liters per minute and air flow rate was between 80-100 Nm 3 /hr.
- the SMD varied between 20 pm to 55 pm.
- these parameters may be tuned for any particular hydrocarbon used as liquid feed and paired with steam or other gas as the vapor phase in such two-fluid nozzles.
- Droplet vaporization time is proportional to square of the droplet diameter.
- the droplets may encounter higher swirl velocities leading to high centrifugal acceleration (e.g., 100 g to 100,000 g forces), resulting in deposition of the droplets on the walls and coking and fouling of the reactor. This creates a positive feedback loop where any deposits will disrupt desirable hydrodynamics and accelerate additional maldistribution and deposition. This leads to coking and plugging of the reactor.
- the droplet characteristics in terms of droplet size, spray angle, etc. are thus important.
- the liquid hydrocarbon feed may have boiling point range from at least, equal to, and/or between any two of 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C, 250
- the liquid hydrocarbon converted with the reactor system 10 can make up from 0.5 wt% to 100 wt% of the total weight of the hydrocarbon reactant feeds (i.e., both liquid and gas hydrocarbons).
- the liquid hydrocarbon may make up from at least, equal to, and/or between any two of 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.
- the liquid hydrocarbon can be converted in the reactor system 10 along with a gaseous hydrocarbon.
- gaseous hydrocarbon or similar expressions is meant to include those hydrocarbons that are at conditions, such as temperature and pressure with or without addition of steam dilution, where the hydrocarbon is in a gaseous or superheated state prior to its introduction into the reactor system 10. This may include those hydrocarbons that may be liquids at standard atmospheric conditions but are at elevated temperatures and/or reduced pressures, such that they are vaporized prior to their introduction into the reactor system 10.
- the gaseous hydrocarbon may include, but is not limited to, natural gas liquids (NGL), a natural gas condensate, a C4 stream, and any one or more of a gaseous Ci to C20 hydrocarbon or mixtures thereof, and combinations of these.
- the gaseous hydrocarbon can include any gaseous hydrocarbon with a boiling point at one atmosphere of about 450 °C, preferably 250 °C, more preferably 150 °C.
- all or a portion of the gaseous hydrocarbon can be cofed with the liquid hydrocarbon feed through the liquid feed inlet 76 and spray nozzle 78.
- the gaseous hydrocarbon may be mixed with the liquid hydrocarbon within the nozzle 78 itself, such as in a mixing chamber of the nozzle, prior to it being discharged as a spray.
- the spray nozzle 78 is not a two-fluid nozzle, the liquid and gaseous hydrocarbons may be mixed and combined upstream of the nozzle 78, where they both may be discharged together through the spray nozzle(s) 78.
- the gaseous hydrocarbon may be introduced separately from the liquid hydrocarbon through the liquid feed inlet 76.
- all or a portion of the gaseous hydrocarbon feed to be converted by the reactor system 10 is introduced through one of the annular gas flow passages 46, 48, 52, 54 of the feed assembly 32. Typically, this will be the upstream flow passage 46, which is immediately adjacent to the liquid feed inlet 76.
- One or both of the liquid hydrocarbon feed and/or gaseous hydrocarbon feed may be mixed with steam. This is typically superheated steam that is combined with and fed with the hydrocarbon feed prior to its introduction into the feed assembly 32 or central chamber 58.
- the steam may be mixed with the liquid hydrocarbon within the nozzle 78 itself prior to it being discharged as a spray. Steam may also be separately introduced into the feed assembly 32 through one of the annular flow passages, such as the downstream flow passage 48.
- a gaseous hydrocarbon feed such as those discussed previously, is introduced from manifold 60 through an inlet into flow passage 46.
- a hydrogen-containing fuel gas is introduced from manifold 66 into flow passage 54.
- the hydrogen-containing fuel gas may be hydrogen gas (H2), methane (CH4), and/or CO/syngas or a combination of these.
- the CH4 is used as fuel for combustion.
- the methane may be present in the fuel gas in an amount from 20 mol%, 15 mol%, 10 mol%, 5 mol% or less. Greater amounts of methane may impact the desired selectivity. In other embodiments, however, greater amounts of methane may be used, including 100% methane for the fuel gas. Natural gas may also be used as fuel gas.
- the hydrogen-containing fuel gas may be a hydrogen-gas-rich stream composed primarily of hydrogen gas, which may be a recycled stream from downstream processing, or additional hydrogen gas.
- the hydrogen-gas-rich stream may contain other components such as methane, CO, steam, inert gases, and CO2.
- Other hydrocarbons can also be used as the fuel gas in certain embodiments and applications. Additionally, small amounts of N2 can also be present.
- Sulfur can also be present in the fuel gas or other feed streams. If sulfur is present, additional separation upstream or downstream may be required.
- the reactor and process are sufficiently robust to accommodate the presence of sulfur, particularly since no catalyst is used.
- the ratio between the hydrocarbon feed (i.e., the total of liquid and gaseous hydrocarbons) to hydrogen-containing fuel will typically range from 1 to 15, more particularly from 1 to 10, based on mass.
- An oxidizer or oxygen-containing gas which may be a concentrated or pure oxygen gas, such as from an air separation unit (not shown), is introduced as the oxidizer feed through manifold 64 through inlets into the flow passage 52. Having the oxygen-containing gas introduced through the downstream flow passage 52 spaces it further from liquid feed inlet 76 and any hydrocarbons gas introduced through flow passage 46 to eliminate or minimize any combustion of the introduced hydrocarbon reactant feeds.
- the mole ratio of H2/O2 may range from 2 to 9, more particularly from 2 to 5, and still more particularly from 2 to 4.
- the oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.2 to 1.0.
- An excess of hydrogen also helps to scavenge free radicals (e.g., O, OOH, OH) formed that would otherwise react with the hydrocarbon feeds.
- a mole ratio of H2/O2 may be less than 2 to compensate for other fuel gases or to have excess O2 in the mixing region to release heat to counter endothermic cracking reactions.
- hydrogen is sub- stoichiometric (below 1) to allow for additional exothermic reactions in the mixing zone.
- the oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.125 to 0.50.
- the ratio between the hydrocarbon feeds to hydrogen fuel will typically range from 1.0 to 15 based on mass depending on the hydrocarbon feed.
- Steam or water may be introduced through manifold 62 and through inlets into the flow passage 48. Steam may be introduced upstream of the other feeds and may be used to cool the walls of the converging-diverging conduit 24 and reactor vessel 12. The introduced steam also reduces the reaction temperatures within the reactor 10. Steam may also be premixed with the various feeds, such as with the liquid and gaseous hydrocarbon feeds, fuel gas, and/or oxygen-containing feed. Steam may be used in a mass ratio of steam-to-fuel from greater than 0 to 10.0, more particularly from 0 to 2.0, in certain applications.
- the operational conditions of the reactor 10 may vary.
- the gas residence time within the reactor 10 may range from 50 milliseconds or less, more particularly from 20 milliseconds or less. In particular embodiments, the residence time may range from 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 millisecond or less, with 10 microseconds being the approximate lowest residence time.
- the pressure at the reactor outlet may vary. A suitable pressure at the reactor outlet may range from 0 kPa (g) to 10,000 kPa (g), more particularly from 0 kPa (g) to 1,000 kPa (g).
- Reaction temperatures may range from 800 °C to 2500 °C where the lowest temperatures are found at the reactor exit when all the endothermic reactions are completed and the highest temperatures are encountered in the combustion regions of the reactor (flame).
- the reaction temperature within the reactor and recirculation zone may range from 900 °C to 1300 °C.
- the temperature within the reactor and recirculation zone may range from 1000 °C to 1300 °C, more particularly from 1200 °C to 1250 °C.
- the reactor temperature is higher than what is achieved in conventional cracking reactors, such as tube furnace reactors, which typically operate at 800 °C to 900 °C.
- the swirling gas mixture facilitates keeping the walls of the reactor much cooler than in such conventional cracking reactors.
- the use of such higher temperatures also allows a shorter residence or contact times shorter contact times resulting in better selectivity and conversion without formation of unwanted products.
- Operating temperatures for the reactor may be selected to avoid excess production of such unwanted compounds, such as CO and CO2, or optimize the olefin-to-acetylene ratio, as acetylene is typically not desired.
- the gases are introduced and flow through the flow passages 46, 48, 52, 54 so that the axial velocity (i.e., relative to the central axis 28) is zero or nearly zero prior to being discharged into the central chamber 58.
- the inlets (not shown) and/or the orientation of the guide vanes 68, 70, 72, 74 may be set for each flow passage 46, 48, 52, 54 so that a selected azimuthal-to-radial velocity ratio for each of the feed streams that flow through the flow passages 46, 48, 52, 54 is achieved, wherein the azimuthal and radial directions are defined in a cross-section perpendicular to the central axis 28 of the reactor 10.
- the radial direction is along a line that extends from the inlet to the central axis 28.
- the azimuthal direction is perpendicular to both this radial direction and the axial direction (i.e., the direction of the central axis 28).
- the azimuthal-to-radial velocity ratio may range from greater than 0 to 30 or more, more particularly from > 0, 1, or 2 to 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.
- the azimuthal-to-radial velocity ratio may range from > 0 to 5, more particularly from 2 to 4.
- the particular azimuthal-to-radial velocity ratio may vary depending upon the particular reactor configuration and composition of the various streams, however. This is more intimately related to the mixing times and reaction times depending on the flow rates, composition of the fuel and feedstocks used for cracking.
- Converted hydrocarbon products produced in the reactor are removed from the reactor vessel 12 through outlet 20.
- the converted hydrocarbon products may be quenched within a quench zone of the reactor 10 or they may be quenched exterior to the reactor 10 in a quenching unit, such as a water-droplet-spray quench vessel, or other suitable gas quench device.
- the quenched products may be further processed and recycled.
- additional hydrocarbon feed gas can be introduced as a secondary feed stream at an intermediate position along the length of reactor vessel 12, such as at inlet 82 (FIG. 1).
- inlet 82 (FIG. 1).
- One or more such inlets 82 may be provided at various locations and in the reactor vessel 12, which may be circumferentially and longitudinally spaced apart.
- the inlets 82 may be oriented or configured so that gases are introduced at an angle, as well, to facilitate swirling fluid flow, similar to that delivered from the inlets of the feed assembly 32.
- Feed assemblies provided on the reactor vessel 12 similar to the feed assembly 32 may be used for the introduction of such cracking feed gas so that the cracking feed is introduced as a swirling fluid flow.
- multiple reactor inlet assemblies and corresponding feed assemblies can be provided in a single reactor while maintaining the high performance.
- the reactor system 10 utilizing the hydrocarbon reactant feeds can be used to provide a variety of higher value products. These include any one or more of olefins, C2 to Ce olefins, ethylene, propylenes, butenes, acetylene, C3 to Ce alkynes, butadienes, aromatic compounds, xylenes, benzene, toluene, and ethyl benzene.
- any one or more of these products, such as C2 to Ce alkanes, xylenes, benzene, and toluene, in the reactor product stream may be separated from the reactor product stream and recycled to form at least a portion of the hydrocarbon reactant feeds.
- FIG. 7 is a plot of selectivity in weight percent of light olefins and aromatics for the conversion of a 20 wt% liquid crude feed and wide range naphtha in the ANJEVOC reactor 10.
- 20 wt% of liquid hydrocarbons with gaseous hydrocarbons to simulate the conversion of liquid and gas products (e.g., NGLs, natural gas condensate, and an associated petroleum gas) produced from oil and gas wells.
- the liquids included distilled Arab light (AL) crude oil (approximately 35-40 wt% heavies removed) and wide range naphtha (WRN).
- AL Arab light
- WRN wide range naphtha
- ANJEVOC reactor 12 were fed with N-butane as the gaseous hydrocarbon into an ANJEVOC reactor, such as the reactor 10 described herein.
- the N-butane gas was introduced through the gas feed 46 of the ANJEVOC reactor 10, while the liquid feed was introduced through the nozzle 78.
- the AL crude oil had a dynamic viscosity of less than 10 cP and was introduced through the liquid feed inlet as a spray non-perpendicularly to the central axis of the central chamber defined surrounded by the feed assembly of the reactor.
- the spray had a SMD size from 10 pm to 130 pm during injection.
- Hydrogen gas was used as the fuel and pure oxygen gas diluted with nitrogen (N2) was used as the oxidizer.
- the fuel and oxidizer were combusted in the central chamber of the reactor to form swirling hot combustion gases for carrying out the cracking reactions.
- Flow rates of hydrogen, N-butane, oxygen and distilled AL or WRN were approximately 4.2, 13.0, 14.6, and 3 Ib/hr, respectively.
- the N-butane was preheated to approximately 350 °C and liquid hydrocarbons of AL and WRN were preheated to approximately 80 °C.
- the N-butane was fed together with approximately 5 Ib/hr of steam.
- FIG. 7 shows selectivity in weight percent of light olefins and aromatics for approximately 20 wt% distilled Arab light crude oil and wide range naphtha with butane for Example 1.
- the selectivity for olefins and aromatics (high value chemicals) varied from 58%- 66%, whereas for C2 olefins (ethylene and acetylene) selectivity varied from 52-62% depending on the operating conditions.
- FIG. 8 shows conversion in percent and bulk gas temperatures in the ANJEVOC reactor 10 for the 20 wt% feeds of AL crude oil and WRN as liquid with butane for Example 1.
- the carbon conversion (“C Conversion”) varied typically between 70% to 90% depending on experimental conditions.
- Bulk gas temperatures were measured at different locations in the reactor ranged between 600 °C - 750 °C.
- the bulk gas temperatures shown in FIG. 8 were measured using different thermocouples located in a plane perpendicular relative to the central axis of the reactor, with the measurements represented by the circular data points being located closer to the central axis of the reactor.
- FIG. 9 shows selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Khuff gas condensate (KGC) crude oil with butane in the ANJEVOC reactor 10.
- KGC Khuff gas condensate
- the butane gas was introduced through the gas feed 46 of the ANJEVOC reactor 10, while the liquid KGC crude oil was introduced through a two-fluid nozzle 78 with nitrogen gas as an atomizing gas.
- the KGC crude oil was introduced as a spray non-perpendicularly to the central axis of the central chamber of the reactor.
- the spray had a SMD size from 10 pm to 130 pm during injection.
- the selectivity in weight percent for olefins and aromatics varied from 60%-67%, whereas for C2 and C3 olefins (ethylene and acetylene and propylene) varied from 56%-61 % depending on the operating conditions.
- H2 flow rate was fixed at 4.2 Ib/hr and O2 flow ranged from 14.4 to 17.6 Ib/hr.
- Total hydrocarbons including KGC and N-butane varied between 16 and 20 Ib/hr.
- Nitrogen (as an atomizing gas) was introduced into the two-fluid nozzle 78 at 20 to 40 psig.
- FIG. 10 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Arab extra light (AXL) crude oil with butane in the ANJEVOC reactor 10.
- the butane gas was introduced through the gas feed 46 of the reactor, while the AXL crude oil was introduced through a two-fluid nozzle 78 as an atomizing gas.
- the AXL crude oil and nitrogen were introduced as a spray non-perpendicularly and non-tangentially to the central axis of the central chamber of the feed assembly of the reactor.
- the spray had a SMD size from 10 pm to 130 pm during injection.
- the weight % selectivity for olefins and aromatics varied from 63%-66%, whereas for C3 olefins (ethylene and acetylene and propylene) varied from 57-59% depending on the operating conditions.
- H2 flow rate was fixed at 4.2 Ib/hr and O2 flow ranged from 14.4 to 17.6 Ib/hr.
- Nitrogen (as an atomizing gas) was introduced into the two-fluid nozzle 78 at 20 to 40 psig.
- Total hydrocarbons including AXL and n-butane varied between 16 and 20 Ib/hr.
- FIG. 11 shows selectivity in weight percent of light olefins and aromatics for either full range pyoil or polybutadiene oligomer with ethane in the ANJEVOC reactor 10.
- the ethane gas was introduced through the gas feed 46 of the reactor, while the pyoil and polybutadiene oligomer were each introduced through the nozzle 78.
- the pyoil and polybutadiene oligomer each had a dynamic viscosity of less than 10 cP.
- the pyoil and polybutadiene oligomer were each introduced as a spray non-perpendicularly and non-tangentially to the central axis of the central chamber of the feed assembly of the reactor.
- the spray had a SMD size from 10 pm to 130 pm during injection.
- the H2 flow rate was fixed at 4.2 Ib/hr and the steam flow rate was fixed at 5 Ib/hr.
- the flow rate of 02 varied from 14.5 to 20 Ib/hr.
- the weight percentage of polybutadiene oligomer and full range pyoil varied between 25 to 50% with respect to the ethane flow.
- the average molecular weight (Mn) of the full range pyoil was 280.
- the average molecular weight (Mn) for polybutadiene was 1,100.
- the overall selectivity for olefins and aromatics ranged between 62 - 67 wt% at a conversion level between 83 and 91%.
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Abstract
A reactor system for converting hydrocarbons includes a feed assembly and an inlet assembly. A feed assembly wall defines a central chamber, and includes multiple flow passages, each to introduce a gas feed into the central chamber in a swirling flow pattern. A circumferential wall of the inlet assembly defines a smoothly-curved converging-diverging conduit in fluid communication with the central chamber. A spray nozzle is positioned relative to the central chamber to introduce a hydrocarbon reactant feed into the central chamber upstream of the conduit in a pattern non-perpendicular to the central axis. A reactor vessel having a reactor wall, which defines a reactor chamber, joins the circumferential wall to the conduit in fluid communication with the reactor chamber. The gas feed and the hydrocarbon reactant feed react in the reactor vessel to convert the hydrocarbon reactant feed into a converted hydrocarbon product, which flows out of the reactor chamber.
Description
HYDROCARBON REACTOR WITH CONSTRICTED NECK PORTION AND
SPRAY NOZZLE
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to each of European patent application no. 23187528.7, filed 25 July 2023, European patent application no. 23187529.5, filed 25 July 2023, European patent application no. 23187530.3, filed 25 July 2023, European patent application no. 23196604.5, filed 11 September 2023, India patent application no. 202341050195, filed 25 July 2023, the entire contents of each of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present disclosure is directed to reactor systems for the production of high value chemical products from liquid hydrocarbons.
BACKGROUND
[0003] Hydrocarbon reactors for oxidative coupling are used in modern chemical processes, for example, for the production of valuable chemicals like olefins. Oxidative coupling of methane (OCM) converts methane into ethylene and other hydrocarbons using catalysts at moderate temperatures and pressures. This process is an alternative to traditional methods due to its potential for higher efficiency and lower environmental impact. Advances in catalyst development and reactor design can further enhance the effectiveness and selectivity of these reactions.
[0004] Pyrolysis reactors are specialized devices used to thermally decompose organic materials in the absence of oxygen. This process, known as pyrolysis, breaks down complex molecules into simpler compounds, producing valuable products like bio-oil, syngas, and char. Common types of pyrolysis reactors include rotary kilns, fluidized beds, fixed beds, and tubular reactors, each suited for different applications and feedstocks. These reactors are widely used in waste management, biofuel production, and the synthesis of carbon materials.
[0005] Hydrocarbon reactors for partial oxidation (POX) are used to convert hydrocarbon feedstocks into syngas, a mixture of hydrogen and carbon monoxide. This process involves reacting the hydrocarbons with a sub-stoichiometric amount of oxygen, meaning less oxygen than required for complete combustion. There are two main types of POX systems: thermal partial oxidation (TPOX) and catalytic partial oxidation (CPOX). Thermal partial oxidation (TPOX) is one type of partial oxidation, which operates at higher temperatures and is suitable
for high sulfur feedstocks. Catalytic partial oxidation (CPOX) is another type of partial oxidation, which uses a catalyst to lower the reaction temperature and is ideal for low sulfur feedstocks. These reactors are used in industries like fuel production and chemical manufacturing.
[0006] Steam crackers are reactors used to break long-chain hydrocarbons and modify smaller alkanes (i.e., naphtha, butane, ethane) into smaller molecules and olefins, such as ethylene and propylene. In such crackers, heavy gases such as naphtha, liquefied petroleum gas (LPG), propane, butane, and ethane are fed into a furnace with steam and converted into smaller olefins. Steam is added to the process to increase the selectivity to olefins with reasonable conversion. Steam crackers operate at high temperatures (i.e., from 750 °C to 900 °C) and have residence times of around 100 to 500 milliseconds. Steam crackers can suffer from heat losses and complexity associated with separate exothermic (combustion in the furnace) and endothermic steps (cracking in the process tubes). The presence of inert compounds in the combustion and process side also affects the overall efficiency. Metallurgical limitations of the reactors also limit the temperatures that can be used. Ideally, higher temperatures with shorter contact times result in better selectivity and conversion to smaller olefins. Steam crackers can also experience plugging from coking, which can increase the capital cost and operational expenses and this also prevents cracking certain heavier feeds. Because commercial crackers are typically optimized for only a certain type of feedstock, feedstock flexibility may also be limited. Typically, these crackers also operate at process pressures less than 200 kPa and that increases the capital cost of the downstream operations.
SUMMARY
[0007] Certain aspects of the subject matter described here can be implemented as a reactor system for converting hydrocarbons. The reactor system includes a feed assembly including a feed assembly wall that defines a central chamber. A central axis of the reactor system passes through the feed assembly. The feed assembly includes multiple flow passages oriented with respect to the central axis. Each flow passage is configured to introduce a gas feed into the central chamber in a swirling flow pattern. The reactor system includes an inlet assembly that includes a circumferential wall that defines a smoothly-curved converging-diverging conduit. The central axis passes through the inlet assembly. The circumferential wall converges towards the central axis and then diverges away from the central axis to define the smoothly-curved converging-diverging conduit. The circumferential wall joins the feed assembly wall to place the smoothly-curved converging-diverging conduit in fluid communication with the central
chamber of the feed assembly. The reactor system includes a spray nozzle positioned relative to the central chamber and configured to introduce a hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit in a pattern nonperpendicular to the central axis. The reactor system includes a reactor vessel that includes a reactor wall that defines a reaction chamber and an outlet. The central axis of the reactor system passes through the reactor vessel. The reactor wall joins the circumferential wall of the feed assembly to join the smoothly-curved converging-diverging conduit in fluid communication with the reactor chamber of the reactor vessel. The smoothly-curved converging-diverging conduit includes a geometry that facilitates recirculation and backflow of fluids within the reactor vessel. The gas feed and the hydrocarbon reactant feed react in the reactor vessel to convert the hydrocarbon reactant feed into a converted hydrocarbon product. The outlet is configured to flow the converted hydrocarbon product out of the reactor chamber.
[0008] An aspect combinable with any other aspect includes the following features. A feed inlet is formed as a length of conduit that joins the feed assembly wall. The spray nozzle is positioned and oriented for introducing the hydrocarbon reactant feed into the central chamber through the feed inlet.
[0009] An aspect combinable with any other aspect includes the following features. The conduit includes an inlet axis that is aligned with the central axis to introduce the hydrocarbon reactant feed axially or non-perpendicularly with respect to the central axis of the central chamber.
[0010] An aspect combinable with any other aspect includes the following features. The feed assembly includes a manifold including the spray nozzle.
[0011] An aspect combinable with any other aspect includes the following features. The manifold includes multiple spray nozzles. Each spray nozzle is configured to introduce the hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit into the reactor vessel in a respective pattern non-perpendicular to the central axis.
[0012] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to introduce the hydrocarbon reactant feed in a non-swirling pattern.
[0013] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to introduce the hydrocarbon reactant feed in a liquid spray flow pattern that is non-parallel to the central axis.
[0014] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to introduce the hydrocarbon reactant feed at a spray angle relative to the
central axis.
[0015] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to introduce the hydrocarbon reactant feed with a Sauter Mean Diameter (SMD) of droplets from 1 pm to 250 pm.
[0016] An aspect combinable with any other aspect includes the following features. The spray nozzle is oriented with respect to the central axis to avoid the liquid feed from being forced by centrifugal forces against the reactor wall.
[0017] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to form droplets with a Dvo.s from 10 microns to 50 microns.
[0018] An aspect combinable with any other aspect includes the following features. The spray nozzle is configured to allow the introduction of two fluids.
[0019] An aspect combinable with any other aspect includes the following features.. A first of the two fluids is a liquid phase fluid. A second of the two fluids is a gas phase fluid.
[0020] An aspect combinable with any other aspect includes the following features. The spray nozzle is a two-fluid spray nozzle.
[0021] An aspect combinable with any other aspect includes the following features. The two- fluid spray nozzle includes a mixing chamber to mix the two different fluids prior to being discharged as a spray.
[0022] An aspect combinable with any other aspect includes the following features. The spray nozzle is not a two-fluid spray nozzle.
[0023] An aspect combinable with any other aspect includes the following features. The two different fluids are mixed and combined upstream of the spray nozzle.
[0024] An aspect combinable with any other aspect includes the following features. The first of the two fluids is the hydrocarbon reactant feed. The second of the two fluids is a gaseous hydrocarbon or steam.
[0025] An aspect combinable with any other aspect includes the following features. Each flow passage includes a respective inlet oriented to impart the swirling flow pattern to the respective gas feed.
[0026] An aspect combinable with any other aspect includes the following features. Each flow passage includes one or more guide vanes oriented to impart the swirling flow pattern to the respective gas feed.
[0027] An aspect combinable with any other aspect includes the following features. The diverging portion of the converging-diverging conduit has an overall angle of divergence from 25° to 55° relative to the central axis.
[0028] An aspect combinable with any other aspect includes the following features. The converging-diverging conduit has a circular cross-section with respect to the central axis.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] For a more complete understanding of the embodiments described herein, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying figures, in which:
[0030] FIG. 1 is an elevational, cross-sectional view of a reactor system for the conversion of liquid plastic-waste-derived pyrolysis oils, waxes, and oligomers in accordance with various embodiments of the disclosure;
[0031] FIG. 2 is a perspective view of a feed assembly of the reactor system of FIG. 1 in accordance with various embodiments of the disclosure;
[0032] FIG. 3 is cross-sectional perspective view of the feed assembly and upstream end of a reaction chamber of the reactor system of FIG. 1;
[0033] FIG. 4 is a plot of the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in a reactor systems, such as that of FIG. 1;
[0034] FIG. 5 is a plot showing the Computational Fluid Dynamics (CFD) calculations of spray evaporation in a reactor, such as that of FIG. 1, wherein all the liquid was vaporized within 5 mm from the injection point; and
[0035] FIG. 6 is a plot of the results of testing of a FLOWMAX® FM3A two-fluid nozzle using liquid water and air showing the various droplet sizes under various flow conditions.
[0036] FIG. 7 is a plot of selectivity in weight percent of light olefins and aromatics for the conversion of a 20 wt% liquid crude feed and wide range naphtha in an ANJEVOC reactor;
[0037] FIG. 8 is a plot of the conversion percentage and bulk gas temperature for the conversion of a 20 wt% liquid crude feed and wide range naphtha in the ANJEVOC reactor;
[0038] FIG. 9 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Khuff gas condensate (KGC) crude oil with butane in the ANJEVOC reactor.
[0039] FIG. 10 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Arab extra light (AXL) crude oil with butane in the ANJEVOC reactor. [0040] FIG. 11 shows selectivity in weight percent of light olefins and aromatics for either full range pyoil or polybutadiene oligomer with ethane in the ANJEVOC reactor.
DETAILED DESCRIPTION
[0041] In various embodiments of the present disclosure, unique reactor technology is described utilized to convert a hydrocarbon product into a converted hydrocarbon product that is or includes high value chemicals, such as light olefins and aromatics. The conversion of these materials may be accomplished in single step of processing or with reduced or minimal processing steps and equipment, as compared to conventional steam cracking processing systems. More specifically, the conversion may be achieved by utilizing ANJEVOC (ANnular JEt VOrtex Chamber) reactor technology that produces annular highly swirled jets of feed gases where hydrogen (or other fuels such as natural gas, recycled syngas, etc.) and oxygen gases are mainly used to generate the heat required for cracking of hydrocarbons. Examples of such ANJEVOC reactors are described in U.S. Patent Nos. 11,020,719 and 11,123,705; and International Publication Nos. W02022/010821A1; W02022/010822A1, and
W02022/010823 Al, each of which is incorporated herein by reference in its entirety for all purposes, including the purpose of illustrating the configuration, construction and operation of such ANJEVOC reactors, and their various components.
[0042] As described below in various embodiments, using a nozzle that creates a particular droplet size and placing the nozzle in a central location within a feed assembly of the reactor system described below (i.e., aligned with or close to the central axis) results in hydrocarbon conversion efficiencies not seen in conventional reactor systems. As described below, the central location of the nozzle injects the liquid hydrocarbon reactant feed into an area of a reactor with a low swirl velocity (e.g., swirl velocity of less than 5 m/s). The location along with the droplet size allows the liquid droplets to vaporize before the droplets enter an area of the feed assembly with higher swirl velocities, thereby preventing rapid coking of the reactor. The combination of a location for the nozzle and a droplet size generated by the nozzle thus provides certain unique advantages.
[0043] The following includes definitions of various terms and phrases used throughout this specification.
[0044] For the purposes of this disclosure, if a numerical value, concentration or range is presented, each numerical value should be read once as modified by the term "about" (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. Also, in the description, it should be understood that an amount range listed or described as being useful, suitable, or the like, is intended that any and every value within the range, including the end points, is to be considered as having been stated. For example, “a range from 1 to 10” is to be read as indicating each and every possible number
along the continuum between about 1 and about 10. Thus, even if specific points within the range, or even no point within the range, are explicitly identified or referred to, it is to be understood that the inventor appreciates and understands that any and all points within the range are to be considered to have been specified, and that inventor possesses the entire range and all points within the range.
[0045] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.
[0046] For the purposes of this disclosure, “X, Y, and/or Z” can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ). Similarly, “at least one of X, Y, and Z” can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ)
[0047] The use of the words “a” or “an” when used in conjunction with the term “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
[0048] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0049] The terms “wt%” or “mol%” refer to a weight or molar percentage of a component, respectively, based on the total weight or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol% of component.
[0050] Referring to FIG. 1, an elevational cross-sectional representation of a reactor system 10 for the conversion of liquid hydrocarbons is shown. The reactor system 10 is configured for the conversion of liquid hydrocarbons in the form of pyoil and waxes and/or oligomers, which may be produced from the pyrolysis of plastic waste, such as MPW, or from other sources. The reactor system 10 can also be used to convert gaseous hydrocarbons in conjunction with the liquid hydrocarbons. The reactor system 10 may constitute an ANJEVOC reactor and includes a reactor vessel 12 having a reactor wall 14 that defines an interior reaction chamber 16. The reactor wall 14 may have a cylindrical configuration with a constant
diameter along all or a portion of its length, which may constitute a majority (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) of its length. In most instances, the reactor vessel 12 is oriented vertically so that the cylindrical reactor wall 14 is oriented in an upright orientation with downward flow. The reactor can have other orientations (e.g., horizontal, sloped, or upright with upward flow), however, because the process is controlled by the centrifugal force, which exceeds the gravitational force by several orders of magnitude. The reactor vessel 12 may be configured to provide a length to diameter ratio (L/D) of at least 2. In particular applications, the L/D ratio may range from 2-10, more particularly from 2-5. [0051] The reactor vessel 12 may be formed from steel. In certain embodiments, a cooling jacket can be provided around all or portions of the reactor vessel 12, wherein a second steel wall 18 is positioned around and spaced from the inner reactor wall 14 and a cooling fluid, such as water, may be circulated through the jacket formed between the walls 14, 18. In other embodiments, the reactor wall 14 may be formed from one or more layers of refractory material that line the interior of an outer steel wall to reduce heat loss and sustain the high temperatures of the reactor 10. Because of the unique design and operation of the reactor 10, the reactor wall 14 is cooled internally by the high-velocity near-wall gas flow pushed by centrifugal forces against the reactor wall 14 so that in some applications no exterior cooling jacket is required. This also allows refractory materials to be used for the interior of the reactor wall 14. Refractory materials (without cooling) typically cannot be used with conventional cracking reactors with pure oxygen due to the higher temperatures (e.g., from 2000 °C to 2800 °C). Reaction temperature for the conversion of liquid hydrocarbons, such as crude oil, in the reactor system 10 will typically range from 800 °C to 2500 °C.
[0052] An outlet 20 is provided at a lower or downstream end of the reactor vessel 12 for removing or discharging cracked products from the reaction chamber 16. The outlet diameter can be same as the diameter of the reactor wall 14 or the outlet diameter may be reduced to accelerate the flow before quenching and collection downstream.
[0053] The reactor 10 includes a reactor inlet assembly 22 that is coupled or joined to the upper or upstream end of the reactor wall 14 of the reactor vessel 12. Here, the reactor vessel 12 is oriented vertically with the inlet assembly 22 located above the reactor vessel 12. This is so that any downstream liquid quenching fluids (e.g., water) that are used within the reaction chamber 16 to quench the reaction gases are carried by gravity to the outlet 20 and not towards the upstream end towards the inlet assembly 22.
[0054] The inlet assembly 22 defines a converging-diverging conduit 24 defined by a circumferential wall 26 that surrounds a central axis 28 of the reactor 10. is the central axis 28
of the reactor 10 may be the same or coincide with the central axis of each of the inlet assembly 22 or conduit 24 and reactor vessel 12. The circumferential wall 26 extends from opposite upstream and downstream ends of the converging-diverging conduit 24. As used herein, the terms “upstream” and “downstream” or similar expressions with respect to describing various components of the reactor system 10 shall refer to the position of the component with respect to the direction of overall fluid flow through the reactor 10 along the central axis 28.
[0055] As can be seen in FIG. 1, the circumferential wall 26 smoothly tapers in width or diameter from the upstream ends to define an annular constricted neck portion located between the downstream and upstream ends of the converging-diverging conduit 24. At the annular constricted neck portion, where the circumferential wall 26 of the conduit 24 transitions from converging or narrowing to diverging or widening, the circumferential wall 26 smoothly expands or diverges in width or diameter downstream from the annular constricted neck portion. The interior of the circumferential wall 26 may have a circular perpendicular transverse cross section with respect to the central axis 28 along all or a portion of its length. The circumferential wall 26 defines an interior flow path of the feed assembly 32, with the constricted neck portion being part of the smoothly curved and streamlined converging-diverging nozzle of the inlet assembly 22.
[0056] The nozzle geometry of the converging-diverging conduit 24 is configured based upon the theory relating to swirling conical jets of a viscous incompressible fluid. This phenomenon is described in the journal article by Pannala et al., entitled "Novel Annular Jet Vortex Reactor for High-Temperature Thermochemical Conversion of Hydrocarbons to Acetylene," published in ACS Engineering in 2022 (Pannala, S. et al. ACS Engineering 2022, 2(5), 406-420). The downstream or diverging portion of the conduit 24 is configured for non- supersonic fluid flow. Conduits or nozzles configured for supersonic flow, such as de Laval nozzles, are configured differently from the conduit 24 to provide supersonic flow downstream to form a shockwave. In various embodiments, the diverging conduit 24 does not form such supersonic flow or shockwave. Instead, the conduit 24 has a geometry that facilitates a recirculation and backflow of gases within the interior reaction chamber 16 near the central axis 28 in combination with annular swirling jet gas flow adjacent to the inner reactor wall 14. As such, the conduit 24 will have a greater angle of divergence than the angle of divergence typically utilized in de Laval nozzles, which have an angle of divergence of 15° or less. In certain embodiments, the overall angle of divergence “A” (FIG. 1) relative to the central axis 28 may be from 25° or more. In particular instances, the angle of divergence A for the diverging portion of the conduit 24 discussed herein is from 25° to 55°. In some
embodiments, the angle of divergence A is from at least, equal to, and/or between any two of 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, 40°, 41°, 42°, 43°, 44°, 45°, 46°, 47°, 48°, 49°, 50°, 51°, 52°, 53°, 54°, and 55°. The large divergence angle leads to recirculation of fluid flow at the reactor wall 14, as a result of the upstream swirling flow coupled with the convergent divergent conduit 24.
[0057] The downstream end of the diverging portion of conduit 24 joins the reactor wall 14 at an inlet of the reaction chamber 16 around its perimeter so that the conduit 24 is in fluid communication with the reaction chamber 16 of the reactor vessel 12. The upstream end of the converging portion of conduit 24 forms an inlet for the reactor vessel 12.
[0058] A reactor feed assembly 32 is provided with the reactor system 10. A perspective view of the feed assembly 32 is shown in FIG. 2. The reactor feed assembly 32 joins the upstream end of conduit 24 and is in fluid communication with the conduit 24, with the central axis 28 passing through the reactor feed assembly 32. The feed assembly 32 includes a downstream feed assembly wall 34 that extends circumferentially around and joins the upstream end of the converging portion of conduit 24. The feed assembly wall 34 or circumferential portions thereof are oriented perpendicularly or substantially perpendicularly (i.e., < 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
[0059] Axially spaced upstream from the downstream wall 34 along the central axis 28 is an upstream feed assembly wall 36. The upstream wall 36 or circumferential portions thereof are oriented perpendicular to or substantially perpendicularly (i.e., < 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
[0060] An upstream gas partition wall 38 and a downstream gas partition wall 40 are axially spaced between the downstream and upstream feed assembly walls 34, 36 and are axially spaced from one another, with the upstream partition wall 38 being positioned upstream from the downstream partition wall 40. The partition walls 38, 40 or circumferential portions thereof are also each oriented perpendicularly to or substantially perpendicularly (i.e., < 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28. Each of the partition walls 38, 40 has a central opening 42, 44, respectively, that surrounds the central axis 28 and is concentric with the convergingdiverging conduit 24. The inner ends of the partition walls 38, 40 defining the openings 42, 44 terminate at a position upstream of the converging-diverging conduit 24. The central openings 42, 44 each have a circular configuration. Other continuously-curved shapes for the
central openings 42, 44 (e.g., oval) may also be used provided such configuration facilitates the swirling of gases to provide the required swirling flow patterns described herein. This shape may also correspond to the cross-sectional shape of the circumferential wall 26 of the converging-diverging conduit 24. In most applications, however, the central openings 42, 44 will be circular in shape. The central openings 42, 44 may have a diameter or width that is the same or slightly different (smaller or larger) than the diameter or width of the constricted neck of the converging-diverging conduit 24 at its narrowest point.
[0061] Referring to FIG. 1, the upstream partition wall 38 defines an annular gas flow passage 46 located between the upstream feed assembly wall 36 and the upstream side of the upstream partition wall 36. In the embodiment shown, the flow passage 46 constitutes an upstream annular hydrocarbon reactant feed inlet flow passage for introducing a gaseous hydrocarbon to be converted, e.g., into high value chemicals such as light olefins and aromatics. Likewise, an annular gas flow passage 48 is defined by the downstream side of the downstream partition wall 40 and the downstream feed assembly wall 34. In the embodiment shown, the flow passage 48 may constitute an annular steam or water inlet flow passage.
[0062] An intermediate partition wall 50 is axially spaced between the downstream gas partition wall 40 and the upstream gas partition wall 38 to define downstream and upstream intermediate annular gas inlet flow passages 52, 54. The intermediate partition wall 50 also has a central opening 56 that surrounds the central axis 28 and is concentric with the converging-diverging conduit 24. The inner ends of the partition wall 50 defining the opening 56 terminate at a position upstream of the converging-diverging conduit 24. The central opening 56 may have a circular configuration. Other shapes for the central opening 56 (e.g., oval) may also be used provided such configuration facilitates the swirling of gases to provide the required swirling flow patterns described herein.
[0063] The intermediate partition wall 50, or circumferential portions thereof, is also oriented perpendicularly to or substantially perpendicularly (i.e., < 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28. In the embodiment shown, the annular flow passage 52 may constitute an oxygen or oxidizing gas flow passage to facilitate combustion. The annular flow passage 54 may constitute a fuel gas (e.g., H2, CH4, syngas or a combination of these) flow passage for introducing a fuel gas for combustion.
[0064] The area between the downstream and upstream feed assembly walls 34, 36 and spaced radially inward from the central openings 42, 44, 56 of the partition walls 38, 44, 50, respectively, forms a central chamber 58 of the feed assembly 32 that surrounds the central
axis 28. The central axis 28 also coincides with and forms a central axis of the central chamber 58 and feed assembly 32.
[0065] This configuration provides flow passages through which gas feeds to be cracked, steam, oxygen gas, and hydrogen-rich fuel for providing combustion heat can each be separately introduced and passed through the flow passages 46, 48, 52, 54, respectively, into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases. The feeds are introduced into the central chamber in a direction that is non-parallel to the central axis 28. To this end, one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) are configured to introduce the feeds into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases. The feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) may be oriented in a direction that is non-parallel to the central axis 28. In some embodiments, one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) may be oriented less than or equal to 5 degrees, less than or equal to 10 degrees, less than or equal to 20 degrees, less than or equal to 30 degrees, less than or equal to 40 degrees from a direction perpendicular the central axis 28.
[0066] The upstream flow passage 46 can act as a gaseous hydrocarbon feed inlet flow passage. A fuel gas feed comprised of an hydrogen-rich gas feed (i.e., H2) may be introduced into one of the first and second adjacent annular fuel gas inlet flow passages 52, 54, with an oxidizer (i.e., O2) or oxygen-containing gas feed being introduced into the other of the flow passages 52, 54. Typically, the fuel and oxygen gas feeds will be introduced into flow passages that are immediately adjacent to one another to facilitate rapid combustion. In certain applications, the downstream flow passage 52 may be used for delivering the oxidizer or oxygen-containing gas and the upstream flow passage 54 will be used for delivering the hydrogen-rich fuel gas. The steam feed may be introduced into the downstream annular steam inlet flow passage 48. In other instances, the various feeds may be altered in sequences within the flow passages 46, 48, 52, 54. For example, any of flow passages 48, 52, 54 can act as a gaseous hydrocarbon feed inlet flow passages. In certain applications, the steam feed may be combined or introduced with one or more of the other feeds. This may include combining the
steam feed with the fuel-gas feed, the oxygen-containing gas feed, or the hydrocarbon gas feed.
[0067] In certain embodiments, one or more of the flow passages 46, 48, 52, 54 may remain idle or be omitted from the feed assembly 32. If a flow passage is omitted, one of the partition walls 38, 40, 50 need not be present and the number of flow passages will be reduced. In such instances, certain feeds may be combined and introduced together, such as the steam feed previously discussed.
[0068] In the illustrated reactor system 10, the flow passages 46, 48, 52, 54 are configured so that the different feeds pass through flow passages perpendicularly or substantially perpendicularly to the central axis 28 in an inwardly swirling fluid flow pattern within said flow passages so that the feeds flow about the central axis 28 within the central chamber 58. The swirling fuel gas and oxidizer feeds combust within the central chamber 58. [0069] In the illustrated reactor system 10, the walls 34, 36, 38, 40, and 50 forming the different flow passages 46, 48, 52, 54 are parallel to one another. However, in other cases, walls 34, 36, 38, 40, and 50 may be non-parallel to one another. The walls 34, 36, 38, 40, and 50 are axially spaced apart to provide the desired volume and flow characteristics for the gases flowing through them. This may be based upon the desired flow rates or linear velocities of each of the feed gases and their relative amounts. For instance, the relative volume of oxygen gas needed for the combustion is typically smaller than the volume of the hydrogen-rich fuel gas needed for the combustion. Therefore, the partition wall 50 may be spaced closer to the downstream partition wall 40 so that the flow passage 54 for the hydrogen fuel is larger and accommodates the greater flow of fuel gas. The particular spacing may depend on fuel gas and oxidizer combination, the desired volume for combustion, and nature of the hydrocarbon feeds.
[0070] Annular gas manifolds 60, 62, 64, 66 are provided around the outer periphery of the flow passages 46, 48, 52, 54, respectively. In an example, the gas manifold 60 may be fluidly coupled to a gaseous hydrocarbon feed source. The manifold 62 may be fluidly coupled to a steam source. The manifold 64 may be fluidly coupled to an oxygen-containing-gas source, such as a pure O2 feed. And the manifold 66 is fluidly coupled to a hydrogen-rich or fuel feed source, such as H2. The manifolds 60, 62, 64, 66 are provided with the reactor feed assembly 32 to facilitate introduction of feed gases into the flow passages 46, 48, 52, 54. In other embodiments, the different feed sources to each manifold may be varied.
[0071] In general, the gas inlets from the manifolds 60, 62, 64, 66 are oriented to generate an inwardly swirling flow of gases within central chamber 58 (e.g., oriented nearly
tangentially with respect to an outer perimeter of the flow passages 46, 48, 52, 54). In other words, the gas inlets direct the incoming flow of gases along paths that extend inwardly from the walls of central chamber 58 but not along a radius of central chamber 58 directly toward the central axis 28 from the inlets. As an aside, one or more inlets may be provided for each flow passage 46, 48, 52, 54. Furthermore, the walls 34, 36, 38, 40, and 50 that form the different flow passages of the feed assembly 32 prevent the gases from flowing axially along the direction of central axis 28 while they are contained within the flow passages 46, 48, 52, 54. The manifolds 60, 62, 64, 66 can be configured as standard manifolds (e.g., snail-like) as may be typically used in vortex devices.
[0072] Referring to FIG. 2, in some embodiments, one or more or all of the flow passages 46, 48, 52, 54 may be provided with a plurality of circumferentially spaced guide vanes 68, 70, 72, 74 (e.g., 10 to 60 guide vanes for each flow passage). Each guide vane 68, 70, 72, 74 may be a planar member that is oriented in a plane that is parallel to the central axis 28 and extends between the walls 34, 36, 38, 40, and 50. The guide vanes 68, 70, 72, 74 may be circumferentially spaced an equal distance from one another. In certain embodiments, the guide vanes 68, 70, 72, 74 may be fixed in place, with the upper and lower side edges of the guide vanes being joined along their lengths or a portion of their lengths to the walls 34, 36, 38, 40, and 50 so that there are no air gaps between the side edges of the vanes 68, 70, 72, 74 and the walls 34, 36, 38, 40, and 50. In other embodiments, however, the guide vanes are movable. In such cases, the upper and lower side edges of the vanes 68, 70, 72, 74 may be closely spaced from the walls 34, 36, 38, 40, and 50 to provide a small clearance to allow movement. The close spacing may minimize air gaps through which gases may pass. Seals may also be used to effectively close these spaces or clearances while allowing movement. In other instances, the vanes 68, 70, 72, 74 may be oriented so that the plane of the vane is in a non-parallel or slanted orientation relative to the central axis 28. In such cases, the side edges may be fixed to the walls 34, 36, 38, 40, and 50 or remain closely spaced from walls 34, 36, 38, 40, and 50 to minimize air gaps. In certain applications, the guide vanes 68, 70, 72, 74 may be configured as airfoils, such as described in U.S. Patent No. 11,123,705.
[0073] In the illustrated reactor system 10, the guide vanes 68, 70, 72, 74 are provided adjacent to the outer perimeter of the flow passages 46, 48, 52, 54 and are spaced in an annular or circular ring pattern near the manifold inlets. In other reactor systems, they may be provided in an annular pattern at other positions located radially inward or further within the interior of the flow passages 46, 48, 52, 54. Alternatively, one or more additional annular sets of guide
vanes may be located radially inward from those located along the outer periphery to facilitate inwardly swirling fluid flow.
[0074] Feed gases from the manifolds 60, 62, 64, 66 are delivered nearly tangentially to the outer perimeter of the central chamber 58, where the guide vanes 68, 70, 72, 74 may direct the gas flow in an inwardly swirling or spiraling fluid flow pattern within the central chamber 58. In some embodiments, the inlets from the manifolds 60, 62, 64, 66 may be oriented or directed to impart the full inwardly swirling fluid flow without the use of or need for guide vanes. In other embodiments, the guide vanes 68, 70, 72, 74 may impart the full swirling flow of the introduced gases, such as in instances where the gas from the manifold inlets may be directed radially toward the central axis 28 or do not impart the full desired swirling flow. In such cases the guide vanes 68, 70, 72, 74 prevent flow directly toward the central axis 28 and direct the flowing gases nearly tangentially with respect to the inner walls of central chamber 58 to provide the inwardly swirling or spiraling fluid flow pattern.
[0075] The guide vanes 68, 70, 72, 74 of each flow passage 46, 48, 52, 54 may be mounted on actuators (not shown) so that they can be selectively movable to various positions to provide a selected inwardly spiraling flow pattern. The guide vanes 68, 70, 72, 74 may be pivotal about an axis that is parallel to the central axis 28 so that the vanes 68, 70, 72, 74 may be moved to various positions.
[0076] The orientation of the vanes 68, 70, 72, 74 and/or the orientation of the inlets of the manifolds 60, 62, 64, 66 of each flow passage will provide swirling or spiraling fluid jet flow that is in the same rotational direction about the central axis 28, i.e., clockwise or counterclockwise. Thus, gases within each of the flow passages will flow clockwise or counterclockwise about the central axis 28. In general, the vanes 68, 70, 72, 74 will all introduce gases at the same angle inner relative to the walls of central chamber 58 to provide the desired swirling fluid flow characteristics. If the vanes 68, 70, 72, 74 are movable, then they will typically be actuated to move in unison or close to unison.
[0077] In an example, oxygen and hydrogen fuel gases from flow passages 52, 54, gaseous hydrocarbon feed from flow passage 46, and steam from flow passage 48 may be discharged into the central chamber 58 of the feed assembly 32. Because the oxygencontaining gas and hydrogen-rich fuel gas are introduced separately from one another and not as mixture, this eliminates safety issues that would otherwise occur if these gases were premixed prior to their introduction into the feed assembly 32. Furthermore, the combustion reaction takes place rapidly, with most of the combustion occurring within a small space within the central chamber 58 where the two streams of oxygen-containing gas and hydrogen-
rich fuel gas from the flow passages 52, 54 are mixed after being discharged from the flow passages 52, 54. The combustible mixture can be ignited, e.g., using a spark, chemicals or pilot flame that extends through the bottom surface or side surfaces of the reactor. Suction from the swirling flow can transport heat from an ignition device to the combustion zone 58 to initiate the ignition.
[0078] The gaseous hydrocarbon feed from the upstream flow passage 46, and steam from flow passage 48 are discharged into the central chamber 58 so that gaseous hydrocarbon feed, steam and heated combustion gases are mixed together and form a swirling gas mixture within the chamber 58. This swirling gas mixture then passes through the convergingdiverging conduit 24 and into the reaction chamber 16 of the reactor vessel 12.
[0079] A liquid feed inlet 76 is also formed in the upstream feed assembly wall 36 for introducing, into the feed assembly 32, all or a portion of the liquid hydrocarbons to be converted by the reactor system 10 into, e.g., high value chemicals such as light olefins and aromatics. In certain embodiments, there may be more than one or multiple liquid feed inlets 76. The liquid feed inlet 76 may be formed as a length of conduit that joins the feed assembly wall 36. The conduit may include an inlet axis that is aligned with and/or parallel to the central axis 28 so that the liquid feeds or a majority (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) of the liquid feeds introduced through the inlet 76 may be introduced axially or at a non-perpendicular angle with respect to the central axis 28 into the central chamber 58. In other words, the liquid feeds introduced through the inlet 76 are not introduced perpendicularly to axis 28. A liquid feed manifold 80 may be used to introduce liquid feeds through the liquid feed inlet 76. The manifold 80 is fluidly coupled to a liquid feed source comprising the liquid hydrocarbon to be converted. The manifold 80 comprises one or more spray nozzles 78 that may be used to introduce the liquid feed as a liquid spray (i.e., a spray of liquid droplets) into the central chamber 58. Where multiple liquid feed inlets 76 are employed, the manifold 80 may comprise multiple spray nozzles 78 positioned and oriented for introducing, into the central chamber 58 through the liquid feed inlets 76, the liquid feed as multiple sprays of droplets. In some embodiments, the droplets in the liquid feed define a non-swirling spray and/or a radially-extending fanned pattern so that all or a portion of the droplets are not parallel to the central axis, but will have axial and radial flow velocity components. Moreover, the droplet pattern may be centered on or close to the central axis where the swirl velocities are lowest. In some embodiments, one or more spray nozzles 78 introduce liquid into the central chamber 58 of the feed assembly 32 where the swirl velocity of the swirling fluid flow is less than 5 m/s during operation of the reactor 10. One or more
spray nozzles may be located within a certain placement radius (“PR”) defined from a point where the central axis 28 intersects a plane defined by the upstream wall 36 of the feed assembly 32. In one embodiment, the PR is no greater than 30% of the radius of the central chamber 58. In other embodiments, the PR is no greater than 20% of the radius of the central chamber 58.
[0080] The combination of axial and radial flow velocity components define a spray pattern that has a low spray angle and keeps the pattern close to the central axis 28. As a result, the droplets are directed primarily axially (e.g., to define a spray angle of 40° or less). Such a spray angle helps ensure that liquid droplets are vaporized before being caught in the swirling gas flow and forced by centrifugal forces against the reactor wall, which can lead to coking. In particular embodiments, the spray pattern may have a spray angle of at least, equal to, and/or between any two of 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°,
20°, 21°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, and 40°. In certain embodiments, the spray pattern may be a solid conical, hollow-conical, linear stream, or flat spray pattern. In various embodiments, the liquid feed inlet 76 is does not include guide vanes, such as the vanes 68, 70, 72, 74, or other structures that may impart a swirling fluid flow to the liquid hydrocarbon before it enters the central chamber 58.
[0081] By introducing the liquid hydrocarbon axially, the atomized spray with liquid droplets is primarily concentrated close to the central axis 28 of the reactor 10 where the swirl velocity is lowest. In effect, the liquid droplets are concentrated at the “eye” of the swirling flow. Higher swirl velocities are encountered away from the central axis 28 or centerline and closer to the walls. These higher swirl velocities could deposit the atomized droplets on the walls and guide vanes causing coking and fouling. The small droplets interact with the counter current flow of the high temperature gases from the combustion and strong recirculation to vaporize the droplets and follow the other hydrocarbon gases to increase heat and crack in the reactor 10.
[0082] The spray nozzle(s) 78 may be selected and/or configured to provide a particular droplet size. The spray nozzle(s) may be constructed or configured to a provide droplets under the selected flow conditions (e.g., pressure, velocity) having a Sauter Mean Diameter (SMD) or D32 from 1 pm to 250 pm. As used herein, the SMD or D32 size is defined as the ratio of droplet volume to the surface area of the droplets in a spray. Droplet measurements may be determined using phase doppler interferometer (PDI) techniques. In particular embodiments, the spray nozzle(s) at the liquid feed inlet 76 may provide a SMD size for the liquid
hydrocarbon feed of from at least, equal to, and/or between any two of 1 p , 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, and 250 pm.
[0083] The smaller the droplet size, the faster the vaporization and less likely the droplets will enter the higher swirl regions of the reactor. The smaller the droplet size, however, there is a higher pressure drop across the nozzle and there is a limit to how fine an atomization can be achieved with the nozzle. Droplet size is therefore a compromise between the two competing requirements. The plot of FIG. 4 shows the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in the reactor. FIG. 5 shows the Computational Fluid Dynamics (CFD) calculations of spray evaporation in the reactor, wherein all the liquid was vaporized within 5 mm from the injection point. The plot shows the volume fraction of liquid of the spray that ranges from approximately 2.5 xlO'5 at its introduction and goes to 0 (which indicates that all the liquid was vaporized).
[0084] Other characteristics of the droplets generated by the spray nozzle(s) 78 may include the weighted average droplet size. Weighted average droplet size may include a mass (volume) median or 50% diameter (Dvo.s), which is the diameter at which 50% of the total volume of droplets are contained in particles with smaller diameters. In certain embodiments, the Dvo.s of the droplets may be from at least, equal to, and/or between any two of 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm,
and 250 pm. In one specific embodiment, the spray nozzle is configured to form droplets with a DVO.5 from 10 pm to 50 pm.
[0085] The Dvo.i is the diameter below which 10% of the total volume of droplets are found. In certain embodiments, the Dvo.i of the spray may be from at least, equal to, and/or between any two of 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm,
110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm. In one specific embodiment, the spray nozzle is configured to form droplets with a Dvo.i from 5 pm to 25 pm.
[0086] The Dvo.9 is the diameter below which 90% of the total volume of droplets are found. In certain instances, the Dvo.9 of the spray may be from at least, equal to, and/or between any two of 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm,
175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, 250 pm, 255 pm, 260 pm, 265 pm, 270 pm, 275 pm,
280 pm, 285 pm, 290 pm, 295 pm, 300 pm, 305 pm, 310 pm, 315 pm, 320 pm, 325 pm, 330 pm, 335 pm, 340 pm, 345 pm, 350 pm, 355 pm, 360 pm, 365 pm, 370 pm, 375 pm, 380 pm,
385 pm, 390 pm, 395 pm, 400 pm, 405 pm, 410 pm, 415 pm, 420 pm, 425 pm, 430 pm, 435 pm, 440 pm, 445 pm, and 450 pm. In one specific embodiment, the spray nozzle is configured to form droplets with a Dvo.9 from 20 pm to 100 pm.
[0087] To facilitate forming a suitable fine spray of the liquid hydrocarbon feed having such small droplet sizes, the liquid hydrocarbon may be modified to have a dynamic viscosity from 0.1 cP to 1000 cP prior to or at its introduction, as measured using ASTM D445, but at the temperature of operation (i.e., the temperature of the liquid hydrocarbon when passed through the nozzle(s)). For example, as discussed below, the liquid hydrocarbon feed may in some cases be preheated to a temperature between 25 °C to 400°C and viscosity measured at
this temperature. The droplet size is approximately proportional to dynamic viscosity to the power of 0.2 and thus lower dynamic viscosity leads to smaller droplet size. Typically, fluids with lower dynamic viscosity also have lower surface tension and the droplet size is approximately correlated to surface tension to the power of 0.5. In certain embodiments, the liquid hydrocarbon may be modified to have a dynamic viscosity from at least, equal to, and/or between any two of 0.1 cP, 0.2 cP, 0.3 cP, 0.4 cP, 0.5 cP, 0.6 cP, 0.7 cP, 0.8 cP, 0.9 cP, 1 cP, 2 cP, 3 cP, 4 cP, 5 cP, 6 cP, 7 cP, 8 cP, 9 cP, 10 cP, 15 cP, 20 cP, 30 cP, 40 cP, 50 cP, 60 cP, 70 cP, 80 cP, 90 cP, 100 cP, 150 cP, 200 cP, 250 cP, 300 cP, 350 cP, 400 cP, 450 cP, 500 cP, 550 cP, 600 cP, 650 cP, 700 cP, 750 cP, 800 cP, 850 cP, 900 cP, 950 cP, and 1000 cP. Modification of the hydrocarbon may include heating the hydrocarbon to a sufficient temperature and/or combining the liquid hydrocarbon with a solvent or low viscosity component to lower the dynamic viscosity. Such solvents may include an oligomer, wax or other liquid have a lower dynamic viscosity than the hydrocarbon being modified.
[0088] In certain applications, the spray nozzle(s) 78 may be configured or selected as a two-fluid nozzle. Such two-fluid nozzles may allow for the introduction of two different fluids, each having different properties from the other. For example, the liquids could include a liquid phase fluid and vapor phase fluid that are each sprayed simultaneously through the nozzle 78. The two-fluid nozzle 78 may have a mixing chamber where the two fluids are mixed prior to being discharged as a spray. Such two-fluid nozzles also provide internal mixing of the two fluids to prevent clogging, as well as providing a fine atomized spray having the above-stated droplet size. Such two-liquid spray nozzles are described, for example, in U.S. Pat. App. Pub. No. US2020/0147624, which is incorporated herein in its entirety for all purposes, including the description of the construction and use of such nozzles. Two-fluid nozzles may facilitate rapidly diffusing the mixture from the outlet, promoting atomization, and forming droplets, which can be conveyed easily by the atomization gas. This can reduce liquid deposition on the mixed gas outlet and prevent clogging. In addition, two-fluid nozzles can help to atomize and disperse high viscosity liquids by flowing a gaseous phase with the high viscosity liquid phase. A suitable commercially available two-fluid nozzle for use as the spray nozzle(s) 78 may include that marketed as the FLOWMAX® X-Series or FLOWMAX® FM3A nozzle, available from Spraying Systems Co., Tokyo, Japan.
[0089] The energy input to the spray nozzle is equal to the pressure drop across the nozzle multiplied by the flow rate. To obtain a targeted droplet size distribution, the choice of single-phase or two-phase nozzle depends on the pressure drop of the nozzles. The selection of a single-phase or two-phase nozzle also depends on various requirements (e.g., (i) spray
angle, (ii) hollow vs. full spray cone, and (iii) internal mixing and external mixing to address fouling, which can be achieved using a two-phase nozzle). Furthermore, for the current application with hydrocarbons, spray nozzle selection may depend on high temperature operability, coking and fouling characteristics, erosion, ability to detect and unplug the narrow openings of the nozzles, etc. In general, two-fluid nozzles provide a broad range of control over the droplet size distribution and ability to self-clean as the vapor phase can be steam. A disadvantage may be that slight variations in vapor phase or liquid phase flow rates or pressures can dramatically vary the droplet and spray characteristics.
[0090] In various embodiments of the present disclosure, the liquid hydrocarbon may be introduced into the liquid feed inlet 76 through the two-fluid spray nozzle 78 along with a gaseous hydrocarbon and/or steam (i.e., superheated steam) as the second fluid. The spray nozzle 78 is coupled to one end of the spray manifold 80 that is fluidly coupled to separate upstream liquid hydrocarbon and gas feed (i.e., steam and/or gaseous hydrocarbons) sources. The range of pressures for the liquid feed versus vapor feed depend on the design of the nozzle. For example, FIG. 6 shows the results of testing of a FLOWMAX® FM3 A two-fluid nozzle using liquid water and air under different flow conditions and the various droplet sizes (i.e., D32, DVO.9, Dvo.99). The liquid pressure was varied in the range of 1-3 barg at a constant gas pressure of 4.14 barg. The corresponding liquid flow was in the range of 1-11 liters per minute and air flow rate was between 80-100 Nm3/hr. For these conditions, the SMD varied between 20 pm to 55 pm. Thus, these parameters may be tuned for any particular hydrocarbon used as liquid feed and paired with steam or other gas as the vapor phase in such two-fluid nozzles. [0091] If the desired droplet characteristics are not achieved, the droplets can take a significantly longer time to vaporize. Droplet vaporization time is proportional to square of the droplet diameter. In addition, the droplets may encounter higher swirl velocities leading to high centrifugal acceleration (e.g., 100 g to 100,000 g forces), resulting in deposition of the droplets on the walls and coking and fouling of the reactor. This creates a positive feedback loop where any deposits will disrupt desirable hydrodynamics and accelerate additional maldistribution and deposition. This leads to coking and plugging of the reactor. For robust operations of the reactor with liquid feed, the droplet characteristics in terms of droplet size, spray angle, etc. are thus important.
[0092] In various embodiments of the present disclosure, the liquid hydrocarbon feed may have boiling point range from at least, equal to, and/or between any two of 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195
°C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C, 250
°C, 255 °C, 260 °C, 265 °C, 270 °C, 275 °C, 280 °C, 285 °C, 290 °C, 295 °C, 300 °C, 305
°C, 310 °C, 315 °C, 320 °C, 325 °C, 330 °C, 335 °C, 340 °C, 345 °C, 350 °C, 355 °C, 360
°C, 365 °C, 370 °C, 375 °C, 380 °C, 385 °C, 390 °C, 395 °C, 400 °C, 405 °C, 410 °C, 415
°C, 420 °C, 425 °C, 430 °C, 435 °C, 440 °C, 445 °C, 450 °C, 455 °C, 460 °C, 465 °C, 470
°C, 475 °C, 480 °C, 485 °C, 490 °C, 495 °C, 500 °C, 505 °C, 510 °C, 515 °C, 520 °C, 525
°C, 530 °C, 535 °C, 540 °C, 545 °C, 550 °C, 555 °C, 560 °C, 565 °C, 570 °C, 575 °C, 580
°C, 585 °C, 590 °C, 595 °C, 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635
°C, 640 °C, 645 °C, and 650 °C.
[0093] The liquid hydrocarbon converted with the reactor system 10 can make up from 0.5 wt% to 100 wt% of the total weight of the hydrocarbon reactant feeds (i.e., both liquid and gas hydrocarbons). In particular embodiments, the liquid hydrocarbon may make up from at least, equal to, and/or between any two of 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, and 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt%, 5.0 wt%, 5.1 wt%, 5.2 wt%, 5.3 wt%, 5.4 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5.8 wt%, 5.9 wt%, 6.0 wt%, 6.1 wt%, 6.2 wt%, 6.3 wt%, 6.4 wt%, 6.5 wt%, 6.6 wt%, 6.7 wt%, 6.8 wt%, 6.9 wt%, 7.0 wt%, 7.1 wt%, 7.2 wt%, 7.3 wt%, 7.4 wt%, 7.5 wt%, 7.6 wt%, 7.7 wt%, 7.8 wt%, 7.9 wt%, 8.0 wt%, 8.1 wt%, 8.2 wt%, 8.3 wt%, 8.4 wt%, 8.5 wt%, 8.6 wt%, 8.7 wt%, 8.8 wt%, 8.9 wt%, 9.0 wt%, 9.1 wt%, 9.2 wt%, 9.3 wt%, 9.4 wt%, 9.5 wt%, 9.6 wt%, 9.7 wt%, 9.8 wt%, 9.9 wt%, and 10.0 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, and 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, and 100 wt% by total weight of the hydrocarbon reactant feedstock.
[0094] In various embodiments of the present disclosure, the liquid hydrocarbon can be converted in the reactor system 10 along with a gaseous hydrocarbon. As used herein,
“gaseous hydrocarbon” or similar expressions is meant to include those hydrocarbons that are at conditions, such as temperature and pressure with or without addition of steam dilution, where the hydrocarbon is in a gaseous or superheated state prior to its introduction into the reactor system 10. This may include those hydrocarbons that may be liquids at standard atmospheric conditions but are at elevated temperatures and/or reduced pressures, such that they are vaporized prior to their introduction into the reactor system 10. The gaseous hydrocarbon may include, but is not limited to, natural gas liquids (NGL), a natural gas condensate, a C4 stream, and any one or more of a gaseous Ci to C20 hydrocarbon or mixtures thereof, and combinations of these. In some embodiments, the gaseous hydrocarbon can include any gaseous hydrocarbon with a boiling point at one atmosphere of about 450 °C, preferably 250 °C, more preferably 150 °C.
[0095] In certain instances, all or a portion of the gaseous hydrocarbon can be cofed with the liquid hydrocarbon feed through the liquid feed inlet 76 and spray nozzle 78. In the case of the liquid hydrocarbon that is introduced using the two-fluid nozzle 78, the gaseous hydrocarbon may be mixed with the liquid hydrocarbon within the nozzle 78 itself, such as in a mixing chamber of the nozzle, prior to it being discharged as a spray. Where the spray nozzle 78 is not a two-fluid nozzle, the liquid and gaseous hydrocarbons may be mixed and combined upstream of the nozzle 78, where they both may be discharged together through the spray nozzle(s) 78. In still other instances, the gaseous hydrocarbon may be introduced separately from the liquid hydrocarbon through the liquid feed inlet 76.
[0096] In many instances, all or a portion of the gaseous hydrocarbon feed to be converted by the reactor system 10 is introduced through one of the annular gas flow passages 46, 48, 52, 54 of the feed assembly 32. Typically, this will be the upstream flow passage 46, which is immediately adjacent to the liquid feed inlet 76.
[0097] One or both of the liquid hydrocarbon feed and/or gaseous hydrocarbon feed may be mixed with steam. This is typically superheated steam that is combined with and fed with the hydrocarbon feed prior to its introduction into the feed assembly 32 or central chamber 58. In the case of the liquid hydrocarbon that is introduced using the two-fluid nozzle 78, the steam may be mixed with the liquid hydrocarbon within the nozzle 78 itself prior to it being discharged as a spray. Steam may also be separately introduced into the feed assembly 32 through one of the annular flow passages, such as the downstream flow passage 48.
[0098] In an example of operation of the reactor system 10, a gaseous hydrocarbon feed, such as those discussed previously, is introduced from manifold 60 through an inlet into flow passage 46. A hydrogen-containing fuel gas is introduced from manifold 66 into flow
passage 54. The hydrogen-containing fuel gas may be hydrogen gas (H2), methane (CH4), and/or CO/syngas or a combination of these. Here, the CH4 is used as fuel for combustion. In certain embodiments where a combination of hydrogen gas and methane are used, the methane may be present in the fuel gas in an amount from 20 mol%, 15 mol%, 10 mol%, 5 mol% or less. Greater amounts of methane may impact the desired selectivity. In other embodiments, however, greater amounts of methane may be used, including 100% methane for the fuel gas. Natural gas may also be used as fuel gas.
[0099] The hydrogen-containing fuel gas may be a hydrogen-gas-rich stream composed primarily of hydrogen gas, which may be a recycled stream from downstream processing, or additional hydrogen gas. The hydrogen-gas-rich stream may contain other components such as methane, CO, steam, inert gases, and CO2. Other hydrocarbons can also be used as the fuel gas in certain embodiments and applications. Additionally, small amounts of N2 can also be present. Sulfur can also be present in the fuel gas or other feed streams. If sulfur is present, additional separation upstream or downstream may be required. The reactor and process are sufficiently robust to accommodate the presence of sulfur, particularly since no catalyst is used. The ratio between the hydrocarbon feed (i.e., the total of liquid and gaseous hydrocarbons) to hydrogen-containing fuel will typically range from 1 to 15, more particularly from 1 to 10, based on mass.
[0100] An oxidizer or oxygen-containing gas, which may be a concentrated or pure oxygen gas, such as from an air separation unit (not shown), is introduced as the oxidizer feed through manifold 64 through inlets into the flow passage 52. Having the oxygen-containing gas introduced through the downstream flow passage 52 spaces it further from liquid feed inlet 76 and any hydrocarbons gas introduced through flow passage 46 to eliminate or minimize any combustion of the introduced hydrocarbon reactant feeds. In certain applications, the mole ratio of H2/O2 may range from 2 to 9, more particularly from 2 to 5, and still more particularly from 2 to 4. The oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.2 to 1.0. An excess of hydrogen also helps to scavenge free radicals (e.g., O, OOH, OH) formed that would otherwise react with the hydrocarbon feeds. In some cases, a mole ratio of H2/O2 may be less than 2 to compensate for other fuel gases or to have excess O2 in the mixing region to release heat to counter endothermic cracking reactions. In some cases, hydrogen is sub- stoichiometric (below 1) to allow for additional exothermic reactions in the mixing zone. The oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.125 to 0.50. Furthermore, the ratio between the hydrocarbon feeds to hydrogen fuel will typically range from 1.0 to 15 based on mass depending on the hydrocarbon feed.
[0101] Steam or water may be introduced through manifold 62 and through inlets into the flow passage 48. Steam may be introduced upstream of the other feeds and may be used to cool the walls of the converging-diverging conduit 24 and reactor vessel 12. The introduced steam also reduces the reaction temperatures within the reactor 10. Steam may also be premixed with the various feeds, such as with the liquid and gaseous hydrocarbon feeds, fuel gas, and/or oxygen-containing feed. Steam may be used in a mass ratio of steam-to-fuel from greater than 0 to 10.0, more particularly from 0 to 2.0, in certain applications.
[0102] In practice, all of the oxygen gas and at least a portion of the hydrogencontaining fuel gas are typically combusted to form heated combustion products that are almost entirely mixed with the other feeds prior to exiting the converging-diverging conduit 24 and entering the reaction chamber 16. With the high centrifugal force of the swirling gases, the denser gases (e.g., cracking feed) flow closer to the reactor wall, while the hotter combustion products tend to flow through the center of the reactor. The device geometry and the swirling gas-mixture from chamber 58 results in a back flow of the gas mixture within the reaction chamber 16. This mixture flows upstream and radially inward from the thin, outer annular mixed gas flow layers circulating within the reaction chamber 16. Internal cooling of the walls may occur due to the high swirling steam delivered through flow passage 48 in FIG. 3. Additional cooling (if necessary) occurs by a water jacket located between walls 14 and 18 in FIG. 1.
[0103] Based upon the type of hydrocarbon feeds, the operational conditions of the reactor 10 may vary. The gas residence time within the reactor 10 may range from 50 milliseconds or less, more particularly from 20 milliseconds or less. In particular embodiments, the residence time may range from 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 millisecond or less, with 10 microseconds being the approximate lowest residence time. The pressure at the reactor outlet may vary. A suitable pressure at the reactor outlet may range from 0 kPa (g) to 10,000 kPa (g), more particularly from 0 kPa (g) to 1,000 kPa (g).
[0104] Reaction temperatures may range from 800 °C to 2500 °C where the lowest temperatures are found at the reactor exit when all the endothermic reactions are completed and the highest temperatures are encountered in the combustion regions of the reactor (flame). The reaction temperature within the reactor and recirculation zone may range from 900 °C to 1300 °C. In particular embodiments, the temperature within the reactor and recirculation zone may range from 1000 °C to 1300 °C, more particularly from 1200 °C to 1250 °C. In some embodiments, the reactor temperature is higher than what is achieved in conventional cracking
reactors, such as tube furnace reactors, which typically operate at 800 °C to 900 °C. As discussed earlier, this is due to the temperature limitations of the metallic materials used for such conventional reactors. In the reactor, the swirling gas mixture facilitates keeping the walls of the reactor much cooler than in such conventional cracking reactors. The use of such higher temperatures also allows a shorter residence or contact times shorter contact times resulting in better selectivity and conversion without formation of unwanted products. Operating temperatures for the reactor may be selected to avoid excess production of such unwanted compounds, such as CO and CO2, or optimize the olefin-to-acetylene ratio, as acetylene is typically not desired.
[0105] The gases are introduced and flow through the flow passages 46, 48, 52, 54 so that the axial velocity (i.e., relative to the central axis 28) is zero or nearly zero prior to being discharged into the central chamber 58. The inlets (not shown) and/or the orientation of the guide vanes 68, 70, 72, 74 may be set for each flow passage 46, 48, 52, 54 so that a selected azimuthal-to-radial velocity ratio for each of the feed streams that flow through the flow passages 46, 48, 52, 54 is achieved, wherein the azimuthal and radial directions are defined in a cross-section perpendicular to the central axis 28 of the reactor 10. In particular, for each inlet, the radial direction is along a line that extends from the inlet to the central axis 28. The azimuthal direction is perpendicular to both this radial direction and the axial direction (i.e., the direction of the central axis 28). Returning to the azimuthal-to-radial velocity ratio, in particular embodiments, it may range from greater than 0 to 30 or more, more particularly from > 0, 1, or 2 to 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some applications the azimuthal-to-radial velocity ratio may range from > 0 to 5, more particularly from 2 to 4. The particular azimuthal-to-radial velocity ratio may vary depending upon the particular reactor configuration and composition of the various streams, however. This is more intimately related to the mixing times and reaction times depending on the flow rates, composition of the fuel and feedstocks used for cracking.
[0106] Converted hydrocarbon products produced in the reactor are removed from the reactor vessel 12 through outlet 20. The converted hydrocarbon products may be quenched within a quench zone of the reactor 10 or they may be quenched exterior to the reactor 10 in a quenching unit, such as a water-droplet-spray quench vessel, or other suitable gas quench device. The quenched products may be further processed and recycled.
[0107] In a variation of the reactor described, additional hydrocarbon feed gas can be introduced as a secondary feed stream at an intermediate position along the length of reactor vessel 12, such as at inlet 82 (FIG. 1). One or more such inlets 82 may be provided at various
locations and in the reactor vessel 12, which may be circumferentially and longitudinally spaced apart. The inlets 82 may be oriented or configured so that gases are introduced at an angle, as well, to facilitate swirling fluid flow, similar to that delivered from the inlets of the feed assembly 32. Feed assemblies provided on the reactor vessel 12 similar to the feed assembly 32 may be used for the introduction of such cracking feed gas so that the cracking feed is introduced as a swirling fluid flow.
[0108] In some embodiments, multiple reactor inlet assemblies and corresponding feed assemblies can be provided in a single reactor while maintaining the high performance.
[0109] The reactor system 10 utilizing the hydrocarbon reactant feeds, such as those described previously, can be used to provide a variety of higher value products. These include any one or more of olefins, C2 to Ce olefins, ethylene, propylenes, butenes, acetylene, C3 to Ce alkynes, butadienes, aromatic compounds, xylenes, benzene, toluene, and ethyl benzene. Furthermore, at least a portion of any one or more of these products, such as C2 to Ce alkanes, xylenes, benzene, and toluene, in the reactor product stream may be separated from the reactor product stream and recycled to form at least a portion of the hydrocarbon reactant feeds.
[0110] The following examples serve to further illustrate various embodiments and applications.
EXAMPLES
[OlH] In the Examples below, different experimental runs were made in an ANJEVOC reactor system 10 as described herein using various liquid hydrocarbons with gaseous hydrocarbons. Each experimental run is shown as a different data point along the x-axes of Figures 7-11.
EXAMPLE 1
[0112] FIG. 7 is a plot of selectivity in weight percent of light olefins and aromatics for the conversion of a 20 wt% liquid crude feed and wide range naphtha in the ANJEVOC reactor 10. Experiments were conducted with 20 wt% of liquid hydrocarbons with gaseous hydrocarbons to simulate the conversion of liquid and gas products (e.g., NGLs, natural gas condensate, and an associated petroleum gas) produced from oil and gas wells. The liquids included distilled Arab light (AL) crude oil (approximately 35-40 wt% heavies removed) and wide range naphtha (WRN). Each of the liquid feeds of AL and WRN (shown in FIG. 12 as “Oil”) were fed with N-butane as the gaseous hydrocarbon into an ANJEVOC reactor, such as the reactor 10 described herein. The N-butane gas was introduced through the gas feed 46 of the ANJEVOC reactor 10, while the liquid feed was introduced through the nozzle 78. The
AL crude oil had a dynamic viscosity of less than 10 cP and was introduced through the liquid feed inlet as a spray non-perpendicularly to the central axis of the central chamber defined surrounded by the feed assembly of the reactor. The spray had a SMD size from 10 pm to 130 pm during injection. Hydrogen gas was used as the fuel and pure oxygen gas diluted with nitrogen (N2) was used as the oxidizer. The fuel and oxidizer were combusted in the central chamber of the reactor to form swirling hot combustion gases for carrying out the cracking reactions. Flow rates of hydrogen, N-butane, oxygen and distilled AL or WRN were approximately 4.2, 13.0, 14.6, and 3 Ib/hr, respectively. The N-butane was preheated to approximately 350 °C and liquid hydrocarbons of AL and WRN were preheated to approximately 80 °C. The N-butane was fed together with approximately 5 Ib/hr of steam.
[0113] FIG. 7 shows selectivity in weight percent of light olefins and aromatics for approximately 20 wt% distilled Arab light crude oil and wide range naphtha with butane for Example 1. The selectivity for olefins and aromatics (high value chemicals) varied from 58%- 66%, whereas for C2 olefins (ethylene and acetylene) selectivity varied from 52-62% depending on the operating conditions.
[0114] FIG. 8 shows conversion in percent and bulk gas temperatures in the ANJEVOC reactor 10 for the 20 wt% feeds of AL crude oil and WRN as liquid with butane for Example 1. The carbon conversion (“C Conversion”) varied typically between 70% to 90% depending on experimental conditions. Bulk gas temperatures were measured at different locations in the reactor ranged between 600 °C - 750 °C. The bulk gas temperatures shown in FIG. 8 were measured using different thermocouples located in a plane perpendicular relative to the central axis of the reactor, with the measurements represented by the circular data points being located closer to the central axis of the reactor.
EXAMPLE 2
[0115] FIG. 9 shows selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Khuff gas condensate (KGC) crude oil with butane in the ANJEVOC reactor 10. The butane gas was introduced through the gas feed 46 of the ANJEVOC reactor 10, while the liquid KGC crude oil was introduced through a two-fluid nozzle 78 with nitrogen gas as an atomizing gas. The KGC crude oil was introduced as a spray non-perpendicularly to the central axis of the central chamber of the reactor. The spray had a SMD size from 10 pm to 130 pm during injection. The selectivity in weight percent for olefins and aromatics (high value chemicals) varied from 60%-67%, whereas for C2 and C3 olefins (ethylene and acetylene
and propylene) varied from 56%-61 % depending on the operating conditions. H2 flow rate was fixed at 4.2 Ib/hr and O2 flow ranged from 14.4 to 17.6 Ib/hr. Total hydrocarbons including KGC and N-butane varied between 16 and 20 Ib/hr. Nitrogen (as an atomizing gas) was introduced into the two-fluid nozzle 78 at 20 to 40 psig.
EXAMPLE 3
[0116] FIG. 10 is a plot of selectivity in weight percent of light olefins and aromatics for approximately 40 wt% Arab extra light (AXL) crude oil with butane in the ANJEVOC reactor 10. The butane gas was introduced through the gas feed 46 of the reactor, while the AXL crude oil was introduced through a two-fluid nozzle 78 as an atomizing gas. The AXL crude oil and nitrogen were introduced as a spray non-perpendicularly and non-tangentially to the central axis of the central chamber of the feed assembly of the reactor. The spray had a SMD size from 10 pm to 130 pm during injection. The weight % selectivity for olefins and aromatics (high value chemicals) varied from 63%-66%, whereas for C3 olefins (ethylene and acetylene and propylene) varied from 57-59% depending on the operating conditions. H2 flow rate was fixed at 4.2 Ib/hr and O2 flow ranged from 14.4 to 17.6 Ib/hr. Nitrogen (as an atomizing gas) was introduced into the two-fluid nozzle 78 at 20 to 40 psig. Total hydrocarbons including AXL and n-butane varied between 16 and 20 Ib/hr.
EXAMPLE 4
[0117] FIG. 11 shows selectivity in weight percent of light olefins and aromatics for either full range pyoil or polybutadiene oligomer with ethane in the ANJEVOC reactor 10. The ethane gas was introduced through the gas feed 46 of the reactor, while the pyoil and polybutadiene oligomer were each introduced through the nozzle 78. The pyoil and polybutadiene oligomer each had a dynamic viscosity of less than 10 cP. The pyoil and polybutadiene oligomer were each introduced as a spray non-perpendicularly and non-tangentially to the central axis of the central chamber of the feed assembly of the reactor. The spray had a SMD size from 10 pm to 130 pm during injection. In all experiments, the H2 flow rate was fixed at 4.2 Ib/hr and the steam flow rate was fixed at 5 Ib/hr. The flow rate of 02 varied from 14.5 to 20 Ib/hr. The weight percentage of polybutadiene oligomer and full range pyoil varied between 25 to 50% with respect to the ethane flow. The average molecular weight (Mn) of the full range pyoil was 280. The average molecular weight (Mn) for polybutadiene was 1,100. The overall selectivity
for olefins and aromatics ranged between 62 - 67 wt% at a conversion level between 83 and 91%.
[0118] These examples show that heavy molecules are rapidly cracked and converted mainly into high value chemicals such as ethylene, acetylene and propylene in the ANJEVOC reactor. Product slates are much cleaner compared to conventional steam crackers. These examples also show that the reactor can directly process high boiling liquid up to approximately 40wt%.
[0119] While the disclosure has been shown in some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes and modifications without departing from the scope of the disclosure based on experimental data or other optimizations considering the overall economics of the process. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the disclosure.
Claims
1. A reactor system for converting hydrocarbons, the reactor system comprising: a feed assembly comprising a feed assembly wall that defines a central chamber, wherein (i) a central axis of the reactor system passes through the feed assembly and (ii) the feed assembly comprises a plurality of flow passages oriented with respect to the central axis, wherein each flow passage is configured to introduce a gas feed into the central chamber in a swirling flow pattern; an inlet assembly comprising a circumferential wall that defines a smoothly-curved converging-diverging conduit, wherein (i) the central axis passes through the inlet assembly, (ii) the circumferential wall converges towards the central axis and then diverges away from the central axis to define the smoothly-curved converging-diverging conduit, and (iii) the circumferential wall joins the feed assembly wall to place the smoothly-curved convergingdiverging conduit in fluid communication with the central chamber of the feed assembly; a spray nozzle positioned relative to the central chamber and configured to introduce a hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit in a pattern non-perpendicular to the central axis; and a reactor vessel comprising a reactor wall that defines a reaction chamber and an outlet, wherein (i) the central axis of the reactor system passes through the reactor vessel and (ii) the reactor wall joins the circumferential wall of the feed assembly to join the smoothly-curved converging-diverging conduit in fluid communication with the reactor chamber of the reactor vessel; wherein the smoothly-curved converging-diverging conduit comprises a geometry that facilitates recirculation and backflow of fluids within the reactor vessel; wherein the gas feed and the hydrocarbon reactant feed react in the reactor vessel to convert the hydrocarbon reactant feed into a converted hydrocarbon product; and wherein the outlet is configured to flow the converted hydrocarbon product out of the reactor chamber.
2. The reactor system of claim 1, further comprising a feed inlet formed as a length of conduit that joins the feed assembly wall, wherein the spray nozzle is positioned and oriented for introducing the hydrocarbon reactant feed into the central chamber through the feed inlet.
3. The reactor system of any one of the preceding claims, wherein the conduit comprises an inlet axis that is aligned with the central axis to introduce the hydrocarbon reactant feed axially or non-perpendicularly with respect to the central axis into the central chamber.
4. The reactor system of any one of the preceding claims, wherein the feed assembly comprises a manifold comprising the spray nozzle.
5. The reactor system of any one of the preceding claims, wherein the manifold comprises a plurality of spray nozzles, each spray nozzle configured to introduce the hydrocarbon reactant feed into the central chamber upstream of the smoothly-curved converging-diverging conduit into the reactor vessel in a respective pattern non-perpendicular to the central axis.
6. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed into the central chamber as a mist.
7. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed into the central chamber as a spray.
8. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed in a non-swirling pattern.
9. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed in a radially-extending fanned pattern.
10. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed in a liquid spray flow pattern that is nonparallel to the central axis.
11. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed at a spray angle relative to the central axis.
12. The reactor system of any one of the preceding claims, wherein the spray angle is 40° or less.
13. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to introduce the hydrocarbon reactant feed with a Sauter Mean Diameter (SMD) of droplets from 1 pm to 250 pm.
14. The reactor system of any one of the preceding claims, wherein the spray nozzle is oriented with respect to the central axis to avoid the liquid feed from being forced by centrifugal forces against the reactor wall.
15. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to form droplets with a Dvo.s from 10 microns to 50 microns.
16. The reactor system of any one of the preceding claims, wherein the spray nozzle is configured to allow the introduction of two fluids.
17. The reactor system of any one of the preceding claims, wherein a first of the two fluids is a liquid phase fluid and a second of the two fluids is a gas phase fluid.
18. The reactor system of any one of the preceding claims, wherein the spray nozzle is a two- fluid spray nozzle.
19. The reactor system of any one of the preceding claims, wherein the two-fluid spray nozzle comprises a mixing chamber to mix the two different fluids prior to being discharged as a spray.
20. The reactor system of any one of the preceding claims, wherein the spray nozzle is not a two-fluid spray nozzle.
21. The reactor system of any one of the preceding claims, wherein the two different fluids are mixed and combined upstream of the spray nozzle.
22. The reactor system of any one of the preceding claims, wherein the first of the two fluids is the hydrocarbon reactant feed and the second of the two fluids is a gaseous hydrocarbon or steam.
23. The reactor system of any one of the preceding claims, wherein each flow passage comprises a respective inlet oriented to impart the swirling flow pattern to the respective gas feed.
24. The reactor system of any one of the preceding claims, wherein each flow passage includes one or more guide vanes oriented to impart the swirling flow pattern to the respective gas feed.
25. The reactor system of any one of the preceding claims, wherein the diverging portion of the converging-diverging conduit has an overall angle of divergence from 25° to 55° relative to the central axis.
26. The reactor system of any one of the preceding claims, wherein the converging-diverging conduit has a circular cross-section with respect to the central axis.
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IN202341050195 | 2023-07-25 | ||
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EP23187528 | 2023-07-25 | ||
EP23187529 | 2023-07-25 | ||
IN202341050195 | 2023-07-25 | ||
EP23187530.3 | 2023-07-25 | ||
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EP23196604.5 | 2023-09-11 | ||
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PCT/EP2024/071069 WO2025021899A1 (en) | 2023-07-25 | 2024-07-24 | Method and reactor for converting liquid hydrocarbons to higher value chemicals |
PCT/EP2024/071070 WO2025021900A1 (en) | 2023-07-25 | 2024-07-24 | Reactor and method for converting liquid hydrocarbons to higher value chemicals |
PCT/EP2024/071072 WO2025021902A1 (en) | 2023-07-25 | 2024-07-24 | Method of converting pyrolysis oils, waxes, and/or oligomers to higher value chemicals |
PCT/EP2024/071219 WO2025021962A1 (en) | 2023-07-25 | 2024-07-25 | Hydrocarbon reactor with constricted neck portion and spray nozzle |
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PCT/EP2024/071069 WO2025021899A1 (en) | 2023-07-25 | 2024-07-24 | Method and reactor for converting liquid hydrocarbons to higher value chemicals |
PCT/EP2024/071070 WO2025021900A1 (en) | 2023-07-25 | 2024-07-24 | Reactor and method for converting liquid hydrocarbons to higher value chemicals |
PCT/EP2024/071072 WO2025021902A1 (en) | 2023-07-25 | 2024-07-24 | Method of converting pyrolysis oils, waxes, and/or oligomers to higher value chemicals |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020086681A2 (en) * | 2018-10-23 | 2020-04-30 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
US20200147624A1 (en) | 2017-07-21 | 2020-05-14 | Spraying Systems Co., Japan | Two-fluid nozzle |
US11020719B2 (en) | 2018-03-07 | 2021-06-01 | Sabic Global Technologies B.V. | Method and reactor for pyrolysis conversion of hydrocarbon gases |
WO2022010821A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Reactor system for the production of high value chemical products |
WO2022010822A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
WO2022010823A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4166830A (en) * | 1978-06-21 | 1979-09-04 | Arand John K | Diacritic cracking of hydrocarbon feeds for selective production of ethylene and synthesis gas |
US12351550B2 (en) * | 2021-03-12 | 2025-07-08 | Sabic Global Technologies B.V. | Separation processes for pyrolysis products of annular jet vortex chamber reactor |
-
2024
- 2024-07-24 WO PCT/EP2024/071071 patent/WO2025021901A1/en unknown
- 2024-07-24 WO PCT/EP2024/071069 patent/WO2025021899A1/en unknown
- 2024-07-24 WO PCT/EP2024/071070 patent/WO2025021900A1/en unknown
- 2024-07-24 WO PCT/EP2024/071072 patent/WO2025021902A1/en unknown
- 2024-07-25 WO PCT/EP2024/071219 patent/WO2025021962A1/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200147624A1 (en) | 2017-07-21 | 2020-05-14 | Spraying Systems Co., Japan | Two-fluid nozzle |
US11020719B2 (en) | 2018-03-07 | 2021-06-01 | Sabic Global Technologies B.V. | Method and reactor for pyrolysis conversion of hydrocarbon gases |
WO2020086681A2 (en) * | 2018-10-23 | 2020-04-30 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
US11123705B1 (en) | 2018-10-23 | 2021-09-21 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
WO2022010821A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Reactor system for the production of high value chemical products |
WO2022010822A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
WO2022010823A1 (en) | 2020-07-06 | 2022-01-13 | Sabic Global Technologies B.V. | Method and reactor for conversion of hydrocarbons |
Non-Patent Citations (2)
Title |
---|
PANNALA ET AL.: "Novel Annular Jet Vortex Reactor for High-Temperature Thermochemical Conversion of Hydrocarbons to Acetylene", ACS ENGINEERING, 2022 |
PANNALA, S. ET AL., ACS ENGINEERING 2022, vol. 2, no. 5, pages 406 - 420 |
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