CN108018069B - A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device - Google Patents
A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device Download PDFInfo
- Publication number
- CN108018069B CN108018069B CN201610973363.2A CN201610973363A CN108018069B CN 108018069 B CN108018069 B CN 108018069B CN 201610973363 A CN201610973363 A CN 201610973363A CN 108018069 B CN108018069 B CN 108018069B
- Authority
- CN
- China
- Prior art keywords
- gas
- regeneration
- reduction
- sulfur
- reducing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 93
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 82
- 230000023556 desulfurization Effects 0.000 title claims abstract description 82
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 80
- 239000011593 sulfur Substances 0.000 title claims abstract description 80
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 69
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 69
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 51
- 239000007789 gas Substances 0.000 claims abstract description 210
- 230000008929 regeneration Effects 0.000 claims abstract description 116
- 238000011069 regeneration method Methods 0.000 claims abstract description 116
- 239000003463 adsorbent Substances 0.000 claims abstract description 76
- 239000012492 regenerant Substances 0.000 claims abstract description 67
- 230000009467 reduction Effects 0.000 claims abstract description 64
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 33
- 239000003638 chemical reducing agent Substances 0.000 claims description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 27
- 239000003546 flue gas Substances 0.000 claims description 18
- 230000001172 regenerating effect Effects 0.000 claims description 16
- 238000011946 reduction process Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000012544 monitoring process Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 4
- 230000000153 supplemental effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000004110 Zinc silicate Substances 0.000 abstract description 13
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 abstract description 13
- 235000019352 zinc silicate Nutrition 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000006722 reduction reaction Methods 0.000 description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 9
- 239000002594 sorbent Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001943 fluorescence-activated cell sorting Methods 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种含硫烃吸附脱硫方法及装置，所述方法包括：脱硫处理：将含硫烃和供氢体与吸附剂混合接触，得到脱硫的含硫烃和载硫的待生剂；再生处理：将所述载硫的待生剂与含氧再生气混合接触，得到再生剂；还原处理：将所述再生剂与还原气体混合接触，得到作为吸附剂循环使用的还原再生剂；该吸附剂中含有活性金属单体，所述还原处理的反应条件包括：以含有非氢还原性气体的气体混合物作为还原气，还原温度为250～420℃，还原压力0～3MPa，还原性气体的体积空速50～1000h‑1，还原时间为0.5～3h。该方法抑制了在还原反应和脱硫反应中硅酸锌的形成，进而改善再生剂的活性和强度。
The invention discloses a sulfur-containing hydrocarbon adsorption desulfurization method and device. The method comprises: desulfurization treatment: mixing and contacting sulfur-containing hydrocarbons and a hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbons and a sulfur-carrying waiting agent Regeneration treatment: mixing and contacting the sulfur-loaded waiting agent with oxygen-containing regeneration gas to obtain a regeneration agent; reduction treatment: mixing and contacting the regeneration agent with a reducing gas to obtain a reducing regeneration agent that is recycled as an adsorbent; The adsorbent contains active metal monomers, and the reaction conditions of the reduction treatment include: a gas mixture containing a non-hydrogen reducing gas is used as the reducing gas, the reduction temperature is 250-420° C., the reduction pressure is 0-3 MPa, and the reducing gas is The volume space velocity is 50～1000h -1 , and the reduction time is 0.5～3h. The method inhibits the formation of zinc silicate in the reduction and desulfurization reactions, thereby improving the activity and strength of the regenerant.
Description
Technical Field
The invention relates to the field of sulfur-containing hydrocarbon desulfurization, in particular to a sulfur-containing hydrocarbon adsorption desulfurization method and a sulfur-containing hydrocarbon adsorption desulfurization device.
Background
With the urgent need of environmental protection, the standards of sulfur content in gasoline/diesel are also decreasing. The gasoline adsorption desulfurization technology (S-Zorb for short) has become an important means for upgrading the quality of oil products. The process has very high sulfur selectivity, small influence on octane number loss, low investment and operation cost and enters an industrial operation stage.
Most of the existing S-Zorb adsorbents are desulfurization adsorbents prepared by using a silicon/aluminum material as a carrier and zinc oxide/active metal (such as nickel) as an active component, and the adsorption activity is reduced due to the formation of carbon deposit and zinc sulfide in the reaction process, so that the regeneration reduction is needed to restore the activity of the adsorbent.
The existing gasoline adsorption desulfurization method mainly comprises the following steps: (1) and (3) desulfurization treatment: mixing and contacting sulfur-containing hydrocarbon and hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbon and a sulfur-carrying spent catalyst; (2) regeneration treatment: mixing and contacting the sulfur-carrying spent regenerant with oxygen-containing regeneration gas to obtain a regenerant; (3) reduction treatment: mixing and contacting the regenerant with a reducing gas to obtain a reducing regenerant which is recycled as an adsorbent; and refluxing the reduction regenerant obtained in the step (3) as an adsorbent to the step (1) to form an adsorbent circulating flow path. As shown in fig. 1, the gasoline adsorption desulfurization device corresponding to the method includes: reactor 1 ', reactor receiver 2 ', lock hopper 3 ', regenerator feed tank 4 ', regenerator 5 ', regenerator receiver 6 ', reducer 7 ' and corresponding connecting lines and valves. Wherein the reactor receiver 2 ' is communicated with a regenerator feed tank 4 ' through a lock hopper 3 ', a spent catalyst outlet at the bottom of the regenerator feed tank 4 ' is connected with a spent catalyst inlet positioned in the middle of the regenerator 5 ' through a conveying pipeline, and a top gas outlet of the regenerator feed tank 4 ' is connected with the regenerator 5 '; the bottom regenerant outlet of the regenerator 5 'is connected with the regenerant inlet of the regenerator receiver 6' through a transfer line, and the top gas outlet of the regenerator receiver 6 'is connected with the regenerator 5'; the regenerator receiver 6 ' is in communication with the reducer 7 ' through lock hopper 3 ' and feeds regenerated sorbent into the reactor 1 ' through reducer 7 '.
However, with continuous cyclic regeneration of the S-Zorb adsorbent, the S-Zorb adsorbent tends to suffer from breakage (decrease in strength) and decrease in activity, which in turn leads to decrease in desulfurization efficiency and increase in consumption.
Disclosure of Invention
The invention aims to provide a sulfur-containing hydrocarbon adsorption desulfurization method and a sulfur-containing hydrocarbon adsorption desulfurization device, so as to improve the activity and strength of a regenerant.
In order to achieve the above object, the present invention provides a method for adsorptive desulfurization of sulfur-containing hydrocarbon, the method comprising: and (3) desulfurization treatment: mixing and contacting sulfur-containing hydrocarbon and hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbon and a sulfur-carrying spent catalyst; regeneration treatment: mixing and contacting the sulfur-carrying spent regenerant with oxygen-containing regeneration gas to obtain a regenerant; reduction treatment: mixing and contacting the regenerant with a reducing gas to obtain a reducing regenerant which is recycled as an adsorbent; the adsorbent contains active metal monomers, and the reaction conditions of the reduction treatment comprise: taking a gas mixture containing non-hydrogen reducing gas as reducing gas, wherein the reducing temperature is 250-420 ℃, the reducing pressure is 0-3 MPa, and the volume space velocity of the reducing gas is 50-1000 h-1。
Meanwhile, in the present invention, there is also provided a sulfur-containing hydrocarbon adsorption desulfurization apparatus comprising: the device comprises a regenerator for regenerating a spent reagent and a reducer for reducing the spent reagent, wherein the regenerator comprises a first regenerator and a second regenerator which are arranged in series along the flow direction of the spent reagent, and a regeneration flue gas outlet of the first regenerator is communicated with a reduction gas inlet of the reducer.
Compared with the method and the device for adsorbing and desulfurizing the sulfur-containing hydrocarbon, the method and the device provided by the invention have the advantages that the gas containing the non-hydrogen reducing gas is used as the reducing gas, the reaction of hydrogen and the oxide of the active metal to form water in the reduction reaction process is avoided, the water partial pressure in the reduction process is effectively reduced, the local water amount in the reduction regenerant is reduced, the formation of zinc silicate in the reduction reaction and the desulfurization reaction is inhibited, and the activity and the strength of the regenerant are further improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic diagram of the structure of a sulfur-containing hydrocarbon adsorption desulfurization unit according to the prior art;
FIG. 2 shows a schematic diagram of the structure of a sulfur-containing hydrocarbon adsorption desulfurization device according to the present invention.
Description of the reference numerals
1 and 1 ' are reactors, 2 and 2 ' are reactor receivers, 3 and 3 ' are lock hoppers, 4 and 4 ' are regenerator feed tanks, 5 ' is a regenerator, 51 is a first regenerator, 52 is a second regenerator, 6 and 6 ' are regenerator receivers, 7 and 7 ' are reducers.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the terms "spent adsorbent", "primary regenerant" and "regenerant" are all adsorbents, and in order to distinguish the different states of the adsorbents, they are named differently according to the process steps of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention. Wherein the term "spent adsorbent" is the adsorbent after the completion of the desulfurization reaction; the term "primary regenerant" is an adsorbent formed after a primary regeneration treatment; the term "regenerant" is the adsorbent obtained after completion of the entire process of the regeneration treatment.
In the present invention, the term "regeneration gas" is a gas used in the regeneration treatment process to promote the oxidation reaction of the spent catalyst; the term "reducing gas" is the gas used to promote the reduction of the regenerant during the reduction process.
In order to improve the activity and consumption problems of the regenerant, particularly the desulfurization adsorbent prepared by using a silicon/aluminum material as a carrier and zinc oxide/active metal (such as nickel) as an active component, the inventors have conducted a great deal of research and found that one of the reasons for the reduction of desulfurization efficiency and the increase of consumption in the desulfurization method by adsorption of sulfur-containing hydrocarbon may be that zinc silicate is inevitably generated during the circulation of the adsorbent, and the formation of zinc silicate reduces the ability of the adsorbent to capture sulfur in the reactor, thereby gradually losing activity, and causing the above problems.
In order to suppress the generation of the zinc silicate component during the circulation of the adsorbent, the inventors have conducted a great deal of research and found that in the conventional sulfur-containing hydrocarbon adsorption desulfurization method, when a hydrogen-containing gas is used as a reducing gas in the step of the reduction reaction, the desulfurization adsorbent prepared using a silicon/aluminum material as a carrier and zinc oxide/nickel as an active component reacts as shown in the following formulas (1) and (2) to form a large amount of water; further, the following problems may be caused: firstly, the water partial pressure in a reducer (reduction treatment) is caused to be too high, so that zinc oxide and silicon dioxide react to form zinc silicate; secondly, the partial water content of the reduction regenerant flowing out of the reducer (reduction treatment) is high, and the reduction regenerant can form zinc silicate during the desulfurization reaction with the sulfur-containing hydrocarbon and the high-temperature regeneration.
(1)H2+NiO＝Ni+H2O；
(2)8H2+Zn3O(SO4)2＝ZnO+2ZnS+8H2O；
For this purpose,in the present invention, there is provided a process for adsorptive desulfurization of sulfur-containing hydrocarbons, which comprises: and (3) desulfurization treatment: mixing and contacting sulfur-containing hydrocarbon and hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbon and a sulfur-carrying spent catalyst; regeneration treatment: mixing and contacting the sulfur-carrying spent regenerant with oxygen-containing regeneration gas to obtain a regenerant; reduction treatment: mixing and contacting the regenerant with a reducing gas to obtain a reducing regenerant which is recycled as an adsorbent; the adsorbent contains active metal monomer (such as Ni or metal element with similar catalytic action to Ni), and the reaction conditions of the reduction treatment comprise: taking a gas mixture containing non-hydrogen reducing gas as reducing gas, wherein the reducing temperature is 250-420 ℃, the reducing pressure is 0-3 MPa, and the volume space velocity of the reducing gas is 50-1000 h-1The reduction time (also called adsorbent retention time) is 0.5-3 h.
Compared with the method for adsorbing and desulfurizing the sulfur-containing hydrocarbon, the method for adsorbing and desulfurizing the sulfur-containing hydrocarbon avoids the reaction of hydrogen and the oxide or the compound of the active metal to form water in the reduction treatment process by adopting the gas containing the non-hydrogen reducing gas as the reducing gas, takes carbon monoxide as an example, the desulfurization adsorbent prepared by taking a silicon/aluminum material as a carrier and zinc oxide/nickel as an active component can react as shown in the following formula (3) and formula (4) in the reduction treatment process, effectively reduces the water partial pressure in the reduction treatment process, reduces the local water amount in the reduction regenerant, inhibits the formation of zinc silicate in the reduction reaction and the desulfurization reaction, and further improves the activity and the strength of the regenerant.
(3)CO+NiO＝Ni+CO2；
(4)8CO+Zn3O(SO4)2＝ZnO+2ZnS+8CO2。
According to the method of the present invention, preferably, the reaction conditions of the reduction treatment include: the reduction temperature is 350-400 ℃, the reduction pressure is 2.4-3 MPa, and the volume space velocity of the reducing gas is 300-500 h-1The reduction time is 1-2 h.
According to the method of the present invention, preferably, the content of the non-hydrogen reducing gas in the reducing gas is 5 to 100 vol%, wherein the reducing gas may be a mixture of the non-hydrogen reducing gas and an inert gas, the inert gas (protective gas) may be one or more of nitrogen, helium, neon and argon, and preferably, the reducing gas is carbon monoxide.
In addition, the inventor also found in the research process that water is also generated in the regeneration treatment step of the existing sulfur-containing hydrocarbon adsorption desulfurization method, and the generation of water causes the following problems: (1) because the oxygen in the regeneration gas reacts with the zinc sulfide to generate zinc oxide and sulfur dioxide, an acid environment is formed in the presence of water, the formation of zinc silicate is further catalyzed in a high-temperature environment, the formation of the zinc silicate can reduce the sulfur capturing capacity of the adsorbent in the reactor, and the adsorbent gradually loses activity; (2) because oxygen in the regenerated gas reacts with zinc sulfide to generate zinc oxide and sulfur dioxide, the sulfur dioxide can be further oxidized into sulfur trioxide; at the moment, the produced water and sulfur trioxide can react to generate sulfuric acid, so that a strong acid environment is formed in the regeneration environment; under this environment, sulphuric acid can react with zinc oxide and generate zinc sulfate, and zinc sulfate has stronger viscidity, can make the adsorbent caking deposit in regenerator bottom, influences the normal cycle of adsorbent. Because the adsorbent in the reaction system can not be normally converted, the sulfur content on the adsorbent is gradually increased, so that the desulfurization of the adsorbent is reduced and reduced, the quality of the product is finally influenced, and even the product can not leave a factory.
To this end, according to the method of the present invention, preferably, the regeneration treatment step includes: and carrying out primary regeneration on the sulfur-carrying spent regenerant at the temperature of 300-480 ℃ to obtain a primary regenerant, and then carrying out secondary regeneration on the primary regenerant at the temperature of 480-580 ℃ to obtain the regenerant.
The method provided by the invention carries out twice regeneration on the spent catalyst, so that coke and hydrocarbon substances carried in the spent catalyst are subjected to condensation reaction in the once regeneration treatment process to form gases such as hydrogen, methane and the like, the hydrogen, the methane and the regenerated gas are promoted to react to form water, and the formed water is discharged along with the regenerated gas; then, carrying out desulfurization reaction on the primary regenerant subjected to primary regeneration treatment in the secondary regeneration treatment process to form a regenerant; in the method, the temperature of the two regenerations is controlled to be low firstly and then high, the water forming environment and the sulfur dioxide forming environment are basically cut, the formation of an acid environment is avoided, the generation of zinc silicate is inhibited, the activity and the strength of the adsorbent can be improved, and the consumption of the adsorbent is greatly reduced.
According to the method of the present invention, preferably, the conditions of the primary regeneration include: the oxygen-containing gas is used as the regeneration gas, the temperature is 300-480 ℃, the pressure is 50-400 kPa, the apparent gas velocity of the regeneration gas is 0.05-0.5 m/s, and the regeneration time (also called the retention time of the adsorbent) is 1-60 min. More preferably, the conditions of the primary regeneration include: using oxygen-containing gas as regeneration gas, the temperature is 330-390 ℃, the pressure is 80-150 kPa, the apparent gas velocity of the regeneration gas is 0.2-0.4 m/s, and the regeneration time is 5-40 min.
According to the method of the present invention, preferably, the conditions of the secondary regeneration include: taking oxygen-containing gas as regeneration gas, wherein the temperature is 480-580 ℃, the pressure is 50-300 kPa, the apparent gas velocity of the regeneration gas is 0.2-0.8 m/s, and the regeneration time is 30-180 min.
The method according to the present invention, wherein the oxygen-containing gas as the regeneration gas has an oxygen content of 0.001 vol% to 42.000 vol%, preferably 10 vol% to 21 vol%, and the oxygen-containing gas may be oxygen, a mixed gas of oxygen and an inert gas (shielding gas), or air. Preferably, the oxygen-containing gas is air. The inert gas (protective gas) can be one or more of nitrogen, helium, neon and argon.
According to the method of the present invention, in order to improve the comprehensive utilization rate of the method, preferably, the regeneration flue gas generated in the primary regeneration process is dried in the reduction treatment and then is used as the reduction gas for reflux. The reaction conditions of the primary regeneration step are controlled, so that the control of the components of the regenerated flue gas generated in the primary regeneration process is facilitated, the part of the regenerated flue gas is mainly inert gas, wherein the carrier is water, carbon monoxide, carbon dioxide and the like, and the content of the carbon monoxide in the regenerated flue gas subjected to drying treatment and moisture removal is more than 5 volume percent, so that the regenerated flue gas is suitable for being used as reducing gas. And the regenerated flue gas is dried and then used as the reducing gas for backflow, so that the use cost of the reducing gas and the treatment cost of the tail gas of the regenerated flue gas can be reduced, and the effect of achieving multiple purposes is achieved.
According to the method of the present invention, preferably, after the regeneration flue gas generated in the primary regeneration process is dried, an appropriate amount of carbon monoxide make-up gas can be further supplemented, and the mixed gas obtained thereby is returned to the reduction treatment step as the reduction gas. The method not only realizes the recycling of the regeneration flue gas generated in the primary regeneration process, but also increases the controllability of the content of the reducing gas in the reducing gas so as to be suitable for different application requirements.
According to the method of the present invention, preferably, the content of carbon monoxide in the reduction off-gas generated during the reduction treatment is monitored, and when the content of carbon monoxide in the reduction off-gas is 5 vol% or more, the reduction off-gas is refluxed and used as a reduction gas; when the content of carbon monoxide in the reduced tail gas is lower than 5 vol%, conveying the reduced tail gas to a subsequent tail gas treatment unit. The method is beneficial to further reducing the use cost of the reducing gas.
The sulfur-containing hydrocarbon adsorption desulfurization method according to the present invention, in which there may be no particular requirement for desulfurization treatment, may refer to conventional processes and conditions in the art, for example, the desulfurization reaction conditions include: the reaction temperature is 300-500 ℃, the reaction pressure is 0.2-10 MPa, the molar ratio of hydrogen to sulfur-containing hydrocarbon is 0.01-1, and the weight hourly space velocity of the sulfur-containing hydrocarbon is 2-10 h-1。
The sulfur-containing hydrocarbon adsorption desulfurization method of the present invention, wherein the hydrogen donor used in the desulfurization treatment process is one or a mixture of two or more selected from hydrogen gas, a hydrogen-containing gas and a hydrogen donor. The hydrogen refers to hydrogen with various purities, and the hydrogen-containing gas is preferably one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas. The volume content of the hydrogen is more than 30 percent, and the hydrogen donor is selected from at least one of tetrahydronaphthalene, decahydronaphthalene and indane.
The sulfur-containing hydrocarbon adsorption desulfurization method according to the present invention, in which there may be no particular requirement for the selection of the adsorbent, is, however, particularly suitable for the desulfurization adsorbent prepared with a silicon/aluminum material as a carrier and a zinc oxide/active metal (e.g., nickel) as an active component to improve the above-mentioned problems of the existing such adsorbents during use. In the present invention, it is preferable that the active metal monomer contained in the adsorbent is Ni, or a metal monomer having a catalytic function similar to Ni, such as iron and cobalt.
Meanwhile, corresponding to the above-mentioned sulfur-containing hydrocarbon adsorption desulfurization method, the present invention also provides a sulfur-containing hydrocarbon adsorption desulfurization apparatus comprising: the regenerator 5 is used for carrying out regeneration treatment on a spent reagent and the reducer 7 is used for carrying out reduction treatment on the spent reagent, wherein the regenerator 5 comprises a first regenerator 51 and a second regenerator 52 which are arranged in series along the flow direction of the spent reagent, and a regeneration flue gas outlet of the first regenerator 51 is communicated with a reduction gas inlet of the reducer 7. The device simple structure through carrying out simple institutional advancement to current device, increases a regenerator that can carry out regeneration treatment can.
According to the apparatus of the present invention, a carbon monoxide make-up port is preferably provided in a flow path between the regeneration flue gas outlet of the first regenerator 51 and the reducing gas inlet of the reducer 7, and the carbon monoxide make-up port is connected to an external carbon monoxide supply device. Through setting up the carbon monoxide tonifying qi mouth that links to each other with external carbon monoxide air feeder, can be convenient for adjust the content of getting into the carbon monoxide in the reducing gas of reduction ware 7 in order to be applicable to different user demands.
According to the device of the present invention, preferably, the tail gas outlet of the reducer 7 is connected with the reducing gas inlet of the reducer 7 through a reducing gas return pipeline; the reducing gas backflow pipeline is provided with a reducing gas content monitoring and controlling part, a tail gas outlet connected with a subsequent tail gas treatment unit is arranged on a pipe section between the reducing gas content monitoring and controlling part and the tail gas outlet, and a switch valve is arranged on a pipe section between the reducing gas content monitoring and controlling part and the reducing gas inlet.
The apparatus according to the present invention, as shown in fig. 2, comprises a reactor 1, a reactor receiver 2, a lock hopper 3, a regenerator feed tank 4, a first regenerator 51, a second regenerator 52, a regenerator receiver 6, a reducer 7 and corresponding connecting lines and valves. Wherein the reactor 1 is connected to a reactor receiver 2 according to the circulation route of the adsorbent, said reactor receiver 2 is connected to a regenerator feed tank 4 through a lock hopper 3, and the regenerator feed tank 4 is connected to said first regenerator 51; the first regenerator 51 is connected with a second regenerator 52; the second regenerator 52 is connected to the regenerator receiver 6, and the regenerator receiver 6 is connected to the reducer 7 through the lock hopper 3; the reducer 7 is connected to the reactor 1.
The structure and connection of the reactor 1, the reactor receiver 2, the lock hopper 3, the regenerator feed tank 4, the regenerator receiver 6 and the reducer 7 in the apparatus according to the present invention may have no special requirements, and the detailed description thereof will be omitted herein with reference to the related information of the conventional fluidized bed apparatus known in the art. Wherein the lock hopper 3 is used for changing the environment of the adsorbent in the process of conveying the adsorbent, and the spent adsorbent and the regenerant share one lock hopper 3 in order to save space. When the lock hopper 3 is used for conveying the spent agent, the spent agent can be changed from a high-pressure hydrogen environment of the reactor receiver to a low-pressure inert environment, and the conveying of the regenerated agent of the lock hopper needs to be stopped; similarly, when the lock hopper is used for conveying the regenerant, the regenerant can be changed from a low-pressure inert atmosphere to a high-pressure hydrogen environment, and the conveying of the regenerant by the lock hopper needs to be stopped.
The invention also provides a method for applying the sulfur-containing hydrocarbon adsorption desulfurization device, which comprises the following steps: inputting the preheated hydrogen and sulfur-containing hydrocarbon into a reactor 1 to contact with an adsorbent for desulfurization treatment, wherein in the desulfurization process, the adsorbent is deactivated due to adsorption saturation and coking generation to obtain a spent catalyst; the spent agent is conveyed into the reactor receiver 2 to be in countercurrent contact with stripping gas (hydrogen) input by a distributor at the bottom of the reactor receiver 2, hydrocarbons carried by the adsorbent are stripped, and the stripped spent agent is conveyed to the lock hopper 3; the spent agent entering the lock hopper 3 is replaced by inert gas, depressurized to a low-pressure state and then conveyed to a regenerator feed tank 4; in the regenerator feed tank 4, the spent catalyst is in countercurrent contact with stripping gas flowing in from a gas distributor at the bottom of the regenerator feed tank 4, the stripping gas is separated by a gas cyclone separator and is settled in a settling space at the upper part of the regenerator feed tank 4, the separated gas enters a subsequent first regenerator 51, and the solid returns to a bed layer; the spent regenerant is conveyed from a regenerator feeding tank 4 to a first regenerator 51 for primary regeneration treatment, coke, hydrocarbons and other hydrogen-containing substances entrained in the spent regenerant are removed to form a primary regenerant, the primary regenerant is conveyed to a second regenerator 52 for secondary regeneration treatment, so as to release sulfur elements adsorbed in the primary regenerant to form a required regenerant, the regenerant is conveyed into a regenerator receiver 6, the regenerant is stripped in the regenerator receiver 6 with stripping gas (inert gas) flowing from a gas distributor at the bottom of the regenerator, oxygen, sulfur dioxide and other substances entrained by the regenerant are removed, the stripped regenerant is conveyed to a lock hopper 3, the regenerant entering the lock hopper 3 is subjected to gas replacement by hydrogen, is conveyed to a reducer 7 after being pressurized to a high-pressure state, and the regeneration gas generated in the first regenerator 51 is taken as reducing gas to flow back to the reducer 7, reducing the active metal oxide in the regenerant, and refluxing the reduced regenerant to the reactor 1 for recycling the adsorbent.
According to the present invention, there is no particular requirement for the conditions of use of the components in the above-mentioned apparatus, and reference can be made to the description of the above-mentioned sulfur-containing hydrocarbon adsorption desulfurization method of the present invention, which will not be described herein again.
The following will further illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization method and apparatus according to the present invention with reference to the specific examples
The composition of the gasolines used in the following examples and comparative examples is shown in table 1:
table 1.
| Item | Analyzing data | Item | Analyzing data |
| Density (20 ℃ C.)/kg.m-3 | 727.3 | Induction period/min | 922 |
| Actual gum/mg. (mL)-1 | 0.34 | Distillation range/. degree.C | |
| Refractive index (20 ℃ C.) | 1.4143 | Initial boiling point | 38.5 |
| Sulfur content/ng. (μ L)-1 | 960.48 | 5％ | 49.0 |
| Mercaptan sulfur content/ng. (μ L)-1 | 10.2 | 10％ | 55.5 |
| Hydrogen sulfide content/ng. (μ L)-1 | 0 | 30％ | 74.7 |
| Octane number (RON/MON) | 93.7/83.6 | 50％ | 97.2 |
| Group composition fallout/%) | 70％ | 124.2 | |
| Saturated hydrocarbons | 44.0 | 90％ | 155.2 |
| Olefins | 41.2 | 95％ | 165.2 |
| Aromatic hydrocarbons | 14.8 | End point of distillation | 185.0 |
The catalysts used in the following examples and comparative examples were FACS-09 produced by the institute of petrochemical science, having the composition shown in table 2 below:
table 2.
| Catalyst commodity brand | FACS～09 |
| Chemical composition, weight% | |
| ZnO(wt％) | 45.7 |
| Ni(wt％) | 15.0 |
| ZnS(wt％) | 0 |
| ZnAl2O4(wt％) | 8.9 |
| Zn2SiO4(wt％) | 0 |
| Apparent density, kg/m3 | 1100 |
| Abrasion index,% by |
2 |
| Sieving the components by weight percent | |
| 0～40μm | 9.8 |
| 40～80μm | 63.9 |
| >80μm | 26.3 |
The sulfur content in the following examples and comparative examples was determined by off-line chromatographic analysis using an agilent GC6890-SCD instrument. Motor Octane Number (MON) and Research Octane Number (RON) of the reaction raw material catalytically cracked gasoline and the product gasoline after the desulfurization catalyst is stabilized were measured by GB/T503-1995 and GB/T5487-1995. The contents of zinc sulfate and zinc silicate were determined by X-ray diffraction (XRD).
The following examples and comparative examples monitor the amount of fresh agent replenished into the apparatus per unit time and convert the adsorbent consumption by calculating the ratio of the amount of fresh agent replenished into the apparatus per unit time to the input amount of gasoline.
Example 1
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: the sulfur-containing hydrocarbon adsorption desulfurization device shown in FIG. 2 was used, and gasoline having a composition shown in Table 1 was used as the sulfur-containing hydrocarbon, and the adsorbent shown in Table 2 was introduced into the sulfur-containing hydrocarbon adsorption desulfurization device to conduct adsorption desulfurization treatment, wherein:
(1) desulfurization process (carried out in reactor 1): the hydrogen is taken as a hydrogen supply medium, the temperature is 410 ℃, the pressure is 2.6MPa, and the weight hourly space velocity of the gasoline is 4h-1Carrying out desulfurization reaction under the desulfurization reaction condition that the molar ratio of the hydrogen donor to the gasoline is 0.4 to obtain desulfurized gasoline and a sulfur-carrying spent catalyst;
(2) regeneration treatment:
primary regeneration treatment (performed in the first regenerator 51): the mixed gas of air and nitrogen (oxygen content is 15 volume percent, preheating temperature is 250 ℃) is taken as a first regenerating gas, and the sulfur-carrying spent agent is regenerated for 30min under the regeneration conditions of 360 ℃, 100kPa and the apparent gas velocity of the first regenerating gas of 0.25m/s to obtain a primary regenerating agent.
Secondary regeneration treatment (performed in second regenerator 52): the mixed gas of air and nitrogen (oxygen content is 15 vol%, preheating temperature is 400 ℃) is taken as second regeneration gas, and the primary regenerant is regenerated for 100min under the regeneration conditions of 520 ℃, 130kPa and the apparent gas velocity of the second regeneration gas of 0.25 m/s.
(3) Reduction process (carried out in reducer 7): the mixed gas (the content of CO is 50 vol%) of the regeneration flue gas and the carbon monoxide make-up gas generated in the primary regeneration process is taken as the reducing gas, the primary regenerant is used at the temperature of 380 ℃, the pressure of 2.8MPa and the volume space velocity of the reducing gas (CO) of 400h-1Reducing for 2 hours under the reducing condition to obtain the reduction regeneration adsorbent.
The above-described apparatus was operated at a gasoline throughput of 10kg/h, and in order to maintain the activity of the adsorbent, 20g of fresh adsorbent was added to the apparatus every 5 days, and 20g of adsorbent was discharged. The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Example 2
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: the differences with reference to example 1 are as follows:
(2) regeneration treatment:
primary regeneration treatment (performed in the first regenerator 51): the mixed gas of air and nitrogen (the oxygen content is 10.5 volume percent, the preheating temperature is 250 ℃) is taken as a first regenerating gas, and the sulfur-carrying spent agent is regenerated for 40min under the regeneration conditions of 330 ℃, 150kPa and the apparent gas velocity of the first regenerating gas of 0.4m/s to obtain a primary regenerating agent.
Secondary regeneration treatment (performed in second regenerator 52): the mixed gas of air and nitrogen (oxygen content is 10.5 vol%, preheating temperature is 400 ℃) is used as second regeneration gas, and the primary regenerant is regenerated for 180min under the regeneration conditions of 480 ℃, 300kPa and the apparent gas velocity of the second regeneration gas of 0.4 m/s.
(3) Reduction process (carried out in reducer 7): the regeneration flue gas (the content of CO is 5 vol%) generated in the primary regeneration process is taken as reducing gas, the primary regenerant is used at the temperature of 350 ℃, the pressure of 2.8MPa and the volume space velocity of the reducing gas (CO) of 300h-1Reducing for 2 hours under the reducing condition to obtain the reduction regeneration adsorbent.
The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Example 3
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: with reference to example 1, the difference is that:
(2) regeneration treatment:
primary regeneration treatment (performed in the first regenerator 51): air (the preheating temperature is 250 ℃) is taken as a first regenerating gas, and the sulfur-carrying spent regenerant is regenerated for 5min under the regeneration conditions of 390 ℃, 80kPa and the apparent gas velocity of the first regenerating gas of 0.2m/s to obtain a primary regenerant.
Secondary regeneration treatment (performed in second regenerator 52): air (preheating temperature is 400 ℃) is used as second regeneration gas, and the primary regenerant is regenerated for 30min under the regeneration conditions of 580 ℃, 50kPa and the superficial gas velocity of the second regeneration gas being 0.2 m/s.
(3) Reduction process (carried out in reducer 7): the mixed gas (the content of CO is 25 vol%) of the regeneration flue gas and the carbon monoxide make-up gas generated in the primary regeneration process is taken as the reducing gas, the primary regenerant is used at the temperature of 400 ℃, the pressure of 3MPa and the volume space velocity of the reducing gas (CO) of 500h-1Reducing for 1h under the reducing condition to obtain the reduced regenerated adsorbent.
The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Example 4
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: with reference to example 1, the difference is that:
primary regeneration treatment (performed in the first regenerator 51): the mixed gas of oxygen and nitrogen (the oxygen content is 30 volume percent, the preheating temperature is 400 ℃) is taken as a first regenerating gas, and the sulfur-carrying spent agent is regenerated for 5min under the regeneration conditions of 480 ℃, 140kPa and the apparent gas velocity of the first regenerating gas of 0.12m/s to obtain a primary regenerating agent.
The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Example 5
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: with reference to example 1, the difference is that:
(3) reduction process (carried out in reducer 7): taking a mixed gas of carbon monoxide and nitrogen (the content of CO is 50 vol%) as a reducing gas, controlling the temperature at 250 ℃, the pressure at 3MPa and the volume space velocity of the reducing gas (CO) at 400h-1Reducing for 1h under the reducing condition to obtain the reduced regenerated adsorbent.
The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Example 6
To illustrate the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization process of the present invention.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: the sulfur-containing hydrocarbon adsorption desulfurization device shown in FIG. 1 was used, and gasoline having a composition shown in Table 1 was used as the sulfur-containing hydrocarbon, and the adsorbent shown in Table 2 was introduced into the sulfur-containing hydrocarbon adsorption desulfurization device to conduct adsorption desulfurization treatment, wherein:
(1) desulfurization process (carried out in reactor 1): the hydrogen is taken as a hydrogen supply medium, the temperature is 410 ℃, the pressure is 2.6MPa, and the weight hourly space velocity of the gasoline is 4h-1Carrying out desulfurization reaction under the condition that the molar ratio of the hydrogen donor to the gasoline is 0.4 to obtain desulfurized gasoline and a sulfur-carrying spent catalyst;
(2) regeneration treatment: (carried out in regenerator 5): the mixed gas of air and nitrogen (oxygen content is 15 volume percent, preheating temperature is 400 ℃) is taken as the regeneration gas, the sulfur-carrying spent regenerant is regenerated for 100min under the regeneration conditions of 520 ℃, 130kPa and the apparent gas velocity of the regeneration gas of 0.4m/s, and the primary regenerant is obtained.
(3) Reduction process (carried out in reducer 7): the mixed gas of carbon monoxide and nitrogen (the content of CO is 50 vol%) is used as reducing gas, the temperature is 380 ℃, the pressure is 2.8MPa, and the volume space velocity of the reducing gas (CO) is 400h-1Reducing for 2 hours under the reducing condition to obtain the reduction regeneration adsorbent.
The above-described apparatus was operated at a gasoline throughput of 10kg/h, and in order to maintain the activity of the adsorbent, 30g of fresh adsorbent was added to the apparatus every 5 days, and 30g of adsorbent was discharged. The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Comparative example 1
For comparison, the beneficial effects of the sulfur-containing hydrocarbon adsorption desulfurization method of the present invention are illustrated.
The sulfur-containing hydrocarbon adsorption desulfurization method comprises the following steps: with reference to example 6, the difference is that:
(3) reduction process (carried out in reducer 7): the method takes 96 volume percent hydrogen as reducing gas, the temperature is 380 ℃, the pressure is 2.8MPa, and the volume space velocity of the reducing gas (CO) is 400h-1Reducing for 2 hours under the reducing condition to obtain the reduction regeneration adsorbent.
The above-described apparatus was operated at a gasoline throughput of 10kg/h, and in order to maintain the activity of the adsorbent, 40g of fresh adsorbent was added to the apparatus every 5 days, and 40g of adsorbent was discharged. The product properties and sorbent consumption after 100 days of plant operation are shown in table 3.
Table 3.
Note:
1. the feed gasoline had a sulfur content of 960ppm, a RON of 93.7 and a MON of 83.6.
2.Δ MON represents the reduction in product MON;
3.Δ RON represents the reduction in product RON;
4. and delta (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.
As can be seen from the data in table 3, compared with comparative example 1 in which the sulfur-containing hydrocarbon adsorption desulfurization method of the prior art is adopted, in examples 1 to 6 in which the sulfur-containing hydrocarbon adsorption desulfurization method provided by the present invention is adopted, the generation amounts of zinc sulfate and zinc silicate in the regenerant are significantly reduced, the consumption of the adsorbent is significantly reduced, the sulfur content of the product gasoline is significantly reduced, and the octane number loss is significantly reduced.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973363.2A CN108018069B (en) | 2016-10-28 | 2016-10-28 | A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973363.2A CN108018069B (en) | 2016-10-28 | 2016-10-28 | A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108018069A CN108018069A (en) | 2018-05-11 |
| CN108018069B true CN108018069B (en) | 2021-03-12 |
Family
ID=62084633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610973363.2A Active CN108018069B (en) | 2016-10-28 | 2016-10-28 | A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108018069B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925807A (en) * | 2022-03-29 | 2023-10-24 | 中国石油天然气集团有限公司 | A moving bed adsorption desulfurization device and method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600839A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | A kind of hydrocarbon oil cracking method |
| CN101683611A (en) * | 2008-09-11 | 2010-03-31 | 中国石油化工股份有限公司 | Method of inhibiting in situ silicate formation in desulfurization sorbents |
| CN101773815A (en) * | 2009-01-08 | 2010-07-14 | 中国石油化工股份有限公司 | silicate-resistant desulfurization sorbent |
| CN102191080A (en) * | 2010-03-11 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering sulfur and olefin content in gasoline |
| CN102380360A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Adsorption and regeneration method of flue gas desulfurization and denitrification adsorbent |
| CN102836699A (en) * | 2012-09-24 | 2012-12-26 | 北京立诚石化技术有限公司 | Regenerating and recycling system and method for S-Zorb waste absorbing agent |
| CN103031143A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for simultaneously removing sulfides in gasoline and liquefied gas through single reactor |
-
2016
- 2016-10-28 CN CN201610973363.2A patent/CN108018069B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600839A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | A kind of hydrocarbon oil cracking method |
| CN101683611A (en) * | 2008-09-11 | 2010-03-31 | 中国石油化工股份有限公司 | Method of inhibiting in situ silicate formation in desulfurization sorbents |
| CN101773815A (en) * | 2009-01-08 | 2010-07-14 | 中国石油化工股份有限公司 | silicate-resistant desulfurization sorbent |
| CN102191080A (en) * | 2010-03-11 | 2011-09-21 | 中国石油化工股份有限公司 | Method for lowering sulfur and olefin content in gasoline |
| CN102380360A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Adsorption and regeneration method of flue gas desulfurization and denitrification adsorbent |
| CN103031143A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for simultaneously removing sulfides in gasoline and liquefied gas through single reactor |
| CN102836699A (en) * | 2012-09-24 | 2012-12-26 | 北京立诚石化技术有限公司 | Regenerating and recycling system and method for S-Zorb waste absorbing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108018069A (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2962435A (en) | Hydrocarbon cracking process and catalyst | |
| CN102839011B (en) | Adsorption desulfurization method | |
| CN103031143B (en) | Method for simultaneously removing sulfides in gasoline and liquefied gas through single reactor | |
| CN103922880B (en) | A kind of successive reaction regenerating unit utilizing sulphurized catalyst to carry out dehydrating alkanes | |
| CN106068253B (en) | A kind of manufacturing method of low-carbon alkene | |
| CN108018069B (en) | A kind of sulfur-containing hydrocarbon adsorption desulfurization method and device | |
| CN112745936B (en) | Desulfurization method for catalytic cracking light product, method and device for producing low-sulfur light oil product through catalytic cracking | |
| CN107999043B (en) | A kind of desulfurization adsorbent regeneration method and sulfur-containing hydrocarbon adsorption desulfurization method and device | |
| CN107474876B (en) | A method and system for adsorption desulfurization of sulfur-containing raw materials | |
| CN108014766B (en) | A desulfurization adsorbent regeneration device and method, and a sulfur-containing hydrocarbon desulfurization reaction system and method | |
| CN101433821A (en) | Sorbent for reducing sulfur content in hydrocarbon oils | |
| CN116064155B (en) | Method and system for deep desulfurization of gasoline | |
| CN114456833B (en) | Desulfurization method and device for catalytic cracking light products and method for producing low-sulfur light oil products | |
| CN103773440B (en) | Pretreatment method of desulfurization adsorbent and desulfurization method of sulfur-containing hydrocarbon feedstock | |
| CN109718663A (en) | A method and device for removing sulfur oxides and/or nitrogen oxides in flue gas | |
| CN107469798B (en) | A kind of regeneration method of sulfur adsorbent | |
| CN105623733B (en) | A kind of desulfurizing method by adsorption of petroleum hydrocarbon | |
| CN103723679B (en) | A kind of heavy oil moving-bed hydrogen production process and reactive system | |
| CN114570437A (en) | Method for removing sulfur in catalyst used for moving bed propane dehydrogenation | |
| CN115678608B (en) | Deep desulfurization method and system for gasoline | |
| CN112745934A (en) | Catalytic cracking light product desulfurization method and device | |
| CN112745938B (en) | Catalytic cracking light product desulfurization and separation method | |
| CN112745937B (en) | Catalytic cracking light product desulfurization method and device | |
| CN112745935B (en) | Catalytic cracking light product desulfurization and separation method and device | |
| CN112745933B (en) | Catalytic cracking light product separation and desulfurization method and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |