CN105107346A - 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 - Google Patents
从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 Download PDFInfo
- Publication number
- CN105107346A CN105107346A CN201510554096.0A CN201510554096A CN105107346A CN 105107346 A CN105107346 A CN 105107346A CN 201510554096 A CN201510554096 A CN 201510554096A CN 105107346 A CN105107346 A CN 105107346A
- Authority
- CN
- China
- Prior art keywords
- product
- aqueous phase
- stream
- vapor
- phase
- 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.)
- Granted
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title abstract description 94
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title abstract description 92
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title abstract description 27
- 229910052921 ammonium sulfate Inorganic materials 0.000 title abstract description 27
- 235000011130 ammonium sulphate Nutrition 0.000 title abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 156
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 117
- 229910001868 water Inorganic materials 0.000 claims abstract description 111
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 34
- 239000008346 aqueous phase Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 8
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims 5
- 239000012074 organic phase Substances 0.000 claims 4
- 239000000908 ammonium hydroxide Substances 0.000 claims 3
- 239000007791 liquid phase Substances 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 230000001112 coagulating effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 82
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 39
- 230000003647 oxidation Effects 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 24
- 239000002023 wood Substances 0.000 description 20
- 240000008042 Zea mays Species 0.000 description 15
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 15
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 15
- 235000005822 corn Nutrition 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000008213 purified water Substances 0.000 description 11
- 239000010907 stover Substances 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 150000004763 sulfides Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 235000015097 nutrients Nutrition 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002029 lignocellulosic biomass Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002364 soil amendment Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/245—Preparation from compounds containing nitrogen and sulfur
- C01C1/246—Preparation from compounds containing nitrogen and sulfur from sulfur-containing ammonium compounds
- C01C1/247—Preparation from compounds containing nitrogen and sulfur from sulfur-containing ammonium compounds by oxidation with free oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/705—Ligands for metal-organic catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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
- C10G2300/1011—Biomass
-
- 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
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- 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
-
- 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
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/08—Jet fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0966—Hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Wood Science & Technology (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Industrial Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
- Treating Waste Gases (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
- Gas Separation By Absorption (AREA)
Abstract
本发明涉及将生物质加工成烃燃料的系统和方法，其包括在加氢热解反应器中加工生物质产生烃燃料和工艺蒸气流和将所述工艺蒸气流冷却到产生水流的冷凝温度。将所述水流送到催化反应器，在其中将其氧化以获得含有氨和硫酸铵的产物流。所得冷却的产物蒸气流包括包含H2、CH4、CO、CO2、氨和硫化氢的不可凝工艺蒸气。
Description
本申请是2012年7月26日提交的题为“从加氢热解产物蒸气中以硫酸铵形式除去硫化氢”的PCT/US2012/048345号发明专利申请的分案申请，原申请进入中国国家阶段获得的国家申请号为201280048542.5。
发明领域
本发明涉及经由与氨(NH3)反应以形成硫化铵而从离开加氢热解反应器的产物蒸气中除去(H2S)的方法。另外，所述方法将硫化氢转化成硫酸铵。
相关技术描述
本发明的方法涉及从离开加氢热解反应器的排出蒸气中除去H2S。加氢热解反应器在本领域中已知。
在商业上，H2S一般在克劳斯成套设备(Clausplant)中经由克劳斯法从蒸气流中除去。在克劳斯法中，将H2S氧化以形成二氧化硫(SO2)且随后使二氧化硫与更多的H2S反应以生成水(H2O)和元素硫。总反应为：
2H2S+O2→S2+2H2O
该方法是公知的，且已经广泛用于石油产品的炼制和重整之中。然而，该方法复杂且常包括多个反应步骤。此外，以分子计，该方法可最有效地施用到含有25%或更多的H2S的物流。如果在克劳斯成套设备中加工含有氨以及H2S的物流，则该氨与该H2S一起被氧化。这并不是期望的，因为氨是该加氢热解过程的潜在有价值的反应产物。
来自加氢热解反应器的显著部分的产物蒸气流包含水蒸气和在大气压力下具有低于70华氏度的沸点的烃。来自加氢热解反应器的产物蒸气必须冷却到周围温度以使得液态烃作为单独的产物流回收。当产物蒸气流冷却时，在产物蒸气流中的水蒸气冷凝以形成液态水，且在产物蒸气流中显著分数的任何H2S和任何NH3溶解在该液态水中。所得水溶液因而含有氨和硫化物化合物。
可使水溶性硫化物化合物与氧气催化反应以形成稳定的硫酸盐化合物的方法公开在Mannangeli等的美国专利5,207,927、Gillespie的美国专利5,470,486中。Marinangeli等教导的方法包括使含有硫化物化合物和氧气二者的水流在其中该溶液的pH为9-12且维持氧与硫的比率大于约5的条件下通过适当的氧化催化剂。Gillespie教导的方法需要维持大于12的pH和大于约4的氧与硫的比率。两种方法都优选金属酞菁，Gillespie优选使用碳载体。因此获得基本不含硫化物化合物的产物流，因为所有的硫化物化合物都已经转化成硫酸盐化合物。
发明概述
在本发明方法的加氢热解反应器中，生物质原料转化成含有以下物质的物流：
1.去氧的可凝烃(性质与汽油、柴油和煤油的性质相应)；
2.不可凝烃蒸气(诸如甲烷、乙烷、丙烷和丁烷)；
3.其他不可凝蒸气(CO2、CO和氢气)；
4.水和可溶于液态水的物质如氨(NH3)和硫化氢(H2S)。
由于在所述生物质原料中存在氮而使得NH3存在于所述加氢热解产物流中。由于在所述生物质原料中存在硫而使得H2S存在于所述加氢热解产物流中。在所述原料中的氮和硫在所述加氢热解反应器中与氢气反应分别形成NH3和H2S。
本发明的一个目的在于提供可从由生物质的加氢热解生成的产物蒸气流中除去硫化氢的方法。在使生物质去氧并转化成包括烃的产物的过程中，氢热解实验已经显示离开所述加氢热解器的蒸气流含有按比例的水蒸气、NH3和H2S，这使得该产物独特地适合其中所述H2S与在水溶液中的NH3结合且随后氧化以形成硫酸铵的工艺。这些实验是原始的(original)，且在所述蒸气流中氮化合物和硫化合物的浓度出乎意料且令人惊奇。这些实验在下文提供的实施例中详细描述。
为了在与本发明相关的加氢热解反应器中进行加氢热解，可将来自所述反应器的某些部分的加氢热解产物流送到蒸汽重整器，且使它们在那里与蒸汽反应以生成氢气。通常，将期望将一些或全部的诸如甲烷、乙烷、丁烷等的不可凝烃蒸气送到所述重整器。随后可将这样获得的氢气引回所述加氢热解反应器，使得加氢热解可继续进行。因此可以降低或消除在与本发明相关的加氢热解过程以外对于氢气源的需要。应注意，每当在原料中存在硫时，H2S将存在于来自所述加氢热解过程的产物蒸气流中，且所述H2S的存在产生几个问题。
在产物蒸气流中的H2S对人类具有高毒性。另外，H2S可使来自加氢热解反应器的产物蒸气的蒸汽重整中所涉及的催化剂中毒。此外，H2S可与NH3反应以生成硫化铵((NH4)2S)，且随后氧化以生成硫酸铵((NH4)2SO4)，硫酸铵是具有作为肥料的显著商业价值的产物。
本发明公开了允许在来自生物质的加氢热解的产物蒸气中所包含的H2S和NH3捕集在水流中的方法。生物质加氢热解实验已经证明与本发明相关的加氢热解方法生成含有水蒸气、H2S和NH3的产物流，它们的量尤其使得可以获得经由转化成(NH4)2SO4而去除H2S的必要条件。在该水流中捕集的基本上全部H2S都与NH3反应以形成(NH4)2S。另外，提供剩余的未反应的NH3并将其溶解在该水流中，以根据需要将水流的pH增加到约12或更高或更低以便随后将(NH4)2S转化成(NH4)2SO4。随后可使该物流在热非催化转化区中与氧气反应以将溶解的(NH4)2S基本转化成(NH4)2SO4和硫代硫酸盐。根据在Gillespie的美国专利5,470,486中公开的方法，可使该物流与氧气和氧化催化剂进一步接触，或者，根据在美国专利5,207,927(Marinangeli等)中公开的方法，可使引入的水流在存在适当催化剂的情况下与氧气反应。通过采用任一技术，在这些专利中教导的pH、氧硫摩尔比、压力、温度和液体每小时空速的范围内，由此获得含有NH3和(NH4)2SO4的水流，且随后可将这些化合物回收并作为肥料出售。用于从含有亚硫酸铵和溶解氨的水流获得硫酸铵的各种方法当前处于使用中，且上文提到的实例用来说明实现该转化现有的已确立的技术。
可回收并作为肥料出售的这些氨衍生化合物可与通过该方法生成的炭混合并粒化以生成用以提供肥料并改进土壤的产品。同样，可被回收并作为肥料出售的通过该方法生成的这些氨衍生化合物可与炭和其他必要土壤养分及矿物混合并粒化以生成用以改善、肥化和改进土壤的产品。本领域技术人员还将显而易见，掺入炭及其他必要土壤养分和矿物的这些氨衍生化合物可制备成随时间释放的制剂以避免在农业装置中重复施用。
还获得已经自其中除去了基本上所有的H2S的产物蒸气流。该蒸气流因此可以多种方式处理，包括作为燃料使用以产生蒸汽或将其引导到蒸汽重整器中。
附图简述
自结合附图采用的以下详述将更好地理解本发明的这些及其他目的和特点：
图1示出了根据本发明的一个优选的实施方案的工艺流程图，其中H2S捕集在含有NH3的一次水流中并在反应器中氧化以形成(NH4)2SO4；
图2示出了根据本发明的一个优选的实施方案的工艺流程图，其中仍然保留在冷却的蒸气产物流中的H2S捕集在吸附床中；
图3示出了根据本发明的一个优选的实施方案的工艺流程图，其中将保留在冷却的蒸气产物流中的H2S捕集并与所述一次水流一起送到氧化反应器中，促进H2S更完全地总体转化成(NH4)2SO4；
图4示出了根据本发明的一个优选的实施方案的工艺流程图，其中含有水、NH3和(NH4)2SO4的处理过的含水产物流在酸性气体汽提器中处理；
图5示出了根据本发明的一个优选的实施方案的工艺流程图，其中在将一次水流引入氧化反应器之前酸-水汽提器从该一次水流中除去NH3和H2S；
图6示出了根据本发明的一个优选的实施方案的工艺流程图，其合并了与冷却的蒸气产物流相关的H2S去除单元和在氧化反应器上游的酸-水汽提器。
本发明优选实施方案的详细描述
图1-6示出了本发明的各种优选的实施方案。图1示出了说明本发明方法的最简单的实施方案的工艺流程图，其中H2S捕集在含有NH3的一次水流中并在反应器中氧化以形成(NH4)2SO4。在该实施方案中的产物流包括主要包含工艺蒸气且含有一些H2S的冷却的蒸气流、主要包含冷凝的烃的液流、主要包含氮气和氧气的第二蒸气流和主要包含水、NH3和(NH4)2SO4的处理过的水流。
图1示出了本发明方法的第一且最基本的实施方案。将生物质111和氢气112引入加氢热解器110，其生成固态碳质产物113(称为炭)和产物蒸气流114。固态产物113主要包含在生物质原料111加氢热解之后剩余的碳质残余物。产物蒸气流114在代表所述加氢热解过程的特征、至少足够高以维持所有成分处于气态的温度下离开加氢热解器110(其可包括单个反应器或串联的多个反应器)。然而，作为所述加氢热解转化过程的特征，该温度也可比该最小值显著更高。产物蒸气流114主要包含：
1.去氧可凝烃(性质与汽油、柴油和煤油的性质相应)；
2.不可凝烃蒸气(诸如甲烷、乙烷、丙烷和丁烷)；
3.其他不可凝蒸气(CO2、CO和H2)；
4.水和可溶于液态水的物质如氨(NH3)和硫化氢(H2S)。
该蒸气流穿过冷凝器120或其他装置或其他装置组，其中该蒸气流的温度降低到基本上所有可凝烃都可作为液流回收的点。此时，产生三个相：冷却的气相、烃相和水相。将含有所有三相的冷却的产物流送到分离器130，其中这三相可分成三个单独的物流。
可凝烃产物流132优选在此回收。最初在热产物蒸气流114中的H2S现在被分开，一些在冷却的蒸气流131中离开该分离器，且一些在一次水流133中。在液态烃流132中还可存在痕量的H2S，但极性H2S分子在该液态烃流中的溶解性最小。
离开该分离器的冷却的蒸气产物流131主要包含H2、不可凝烃、CO2、CO和H2S。
离开该分离器的一次水流133主要包含水、NH3和硫化铵((NH4)2S)。在该物流中的(NH4)2S在来自该蒸气流的H2S进入该水流并与NH3反应时生成，其也溶解于该水流中。本发明的一个目的在于以使得一次水流133的pH为约12的方式控制本发明的方法，意思是在该水流中NH3(作为NH4OH)的浓度足够大以生成强碱性溶液。这是有帮助的，在某种程度上有助于稳定H2S且增加其在水流中的溶解性。它对于氧化反应器140的操作也是一个优选的条件，在氧化反应器140中将(NH4)2S氧化以生成(NH4)2SO4。
随后将来自分离器130的一次水流133引入在本文中也称作催化反应器的氧化反应器140。还将空气流141引入该氧化反应器，其量足以对于每摩尔硫供应约5摩尔的氧气。在适当温度和压力下在存在适当催化剂的情况下反应且历时足够的停留时间之后，在一次水流133中的(NH4)2S基本完全氧化。
根据本发明方法的该第一实施方案，处理过的含水产物流142优选自该氧化反应器获得，其包含NH3、液态水和(NH4)2SO4。另外，反应器气体产物流143自该氧化反应器获得，主要包含氮气和未使用的氧气且含有痕量的NH3和水蒸气。应该注意到，在该第一实施方案中，显著浓度的H2S仍然存在于离开分离器单元130的冷却的产物蒸气流131中。
图2为图示本发明方法的一个实施方案的工艺流程图，其中仍然存在于冷却的蒸气产物流中的H2S捕集在吸附床中。在这种情况下，基本完成了保留在冷却的产物蒸气流中的H2S的去除。
图2图示本发明方法的第二实施方案。在该第二实施方案中，在分离器230的下游增加了H2S去除单元250。一次冷却的蒸气产物流231通过H2S去除单元250(其可包括吸附床、液体洗涤或其他类似设备)。在一次冷却的蒸气产物流231中的H2S自一次冷却的蒸气产物流231基本完全除去，且获得主要包含H2、CO、CO2和不可凝烃蒸气的二次冷却的蒸气产物流251。在该实施方案中，该H2S并未回收，且例如将在H2S去除单元250在含H2S的废物适当丢弃的情况下再生时被抛掉。
图3图示本发明方法的第三实施方案。在该第三实施方案中，如上文在第二实施方案中所述，在分离器330的下游增加了H2S去除单元350。一次冷却的蒸气产物流331通过H2S去除单元350(其可包括可重复使用的吸附床、胺涤气器或某些类似设备)。在一次冷却的蒸气产物流331中的H2S被基本完全除去，且获得主要包含H2、CO、CO2和不可凝烃蒸气的二次冷却的蒸气产物流351。然而，在该第三实施方案中，H2S从H2S去除单元350在主要包含气态H2S的物流352中回收且与一次水流333一起送到氧化反应器340。在该氧化反应器中，气态H2S物流352与一次水流333和适当的催化剂接触并形成(NH4)2S，随后将(NH4)2S氧化以形成(NH4)2SO4。以此方式，获得仅含有痕量的H2S且主要包含H2、不可凝烃、CO2和CO的二次冷却的产物蒸气流351。另外，H2S的总体转化率增加，且其比在上文所述的本发明方法的第一实施方案中高。
图4图示本发明方法的第四实施方案。氨(NH3)是潜在有价值的产物，且在本发明方法的第四实施方案中在酸-水汽提器460中将其从离开氧化反应器440的一次处理过的水流442中分离。该方法允许回收主要包含NH3的气流461，而水和(NH4)2SO4自酸-水汽提器在二次处理过的水流462中单独地回收。(NH4)2SO4为高度水溶性的，且(NH4)2SO4的水溶液具有作为农业肥料的潜在价值。如果需要，则该溶液可通过进一步加热二次处理过的水流462来浓缩，这可馏出在该物流中的一些或所有水。
图5图示本发明方法的第五实施方案。该实施方案以在氧化反应器540上游的酸-水汽提器560为特点，酸-水汽提器560从分离器接受一次水流533。水、NH3和H2S及通过NH3与H2S的反应形成的任何(NH4)2S在酸-水汽提器560中除去且作为气流562离开酸-水汽提器。由此生成纯化的液态水流561。该纯化的水流561随后作为产物流得到。如果需要，则可使该纯化的水流561的一部分与来自酸-水汽提器的NH3及H2S的气流562接触。在这种情况下，该NH3和H2S返回溶解在该部分液态水流561中，形成(NH4)2S，且随后将该溶液引入氧化反应器540，以便转化成(NH4)2SO4。然而，优选不使该纯化的水流与气流562返回接触且优选根据需要将物流562冷却，以使得在该物流中的水冷凝且在该物流中的NH3和H2S回到溶液中，形成(NH4)2S，且随后将该溶液引入氧化反应器540中，以便转化成(NH4)2SO4。该方法使得可以得到纯化的水流561且在氧化反应器540的出口处产生水、NH3和(NH4)2SO4的浓缩的处理流542。
图6图示本发明方法的第六实施方案。该实施方案以在氧化反应器640上游的酸-水汽提器660为特点，其从分离器630接受一次水流633。该实施方案还以在分离器630下游的H2S去除单元650为特点，如在上文所述的第三实施方案中。一次冷却的蒸气产物流631通过H2S去除单元650(其可包括吸附床、胺涤气器或某些类似设备)。在一次冷却的蒸气产物流631中的H2S被基本完全除去，且获得主要包含H2、CO、CO2和不可凝烃蒸气的二次冷却的产物蒸气流651。如在第三实施方案中，将H2S回收在主要包含气态H2S的物流652中且将其送到氧化反应器640。
如上文在第五实施方案的描述中所述，在酸-水汽提器660中将溶解的NH3和H2S及通过NH3与H2S的反应形成的任何(NH4)2S驱逐出一次水流633。水、NH3和H2S及通过NH3与H2S的反应形成的任何(NH4)2S在酸-水汽提器660中除去且作为气流662离开该酸-水汽提器。由此生成纯化的水流661。该纯化的水流661随后作为产物流得到。如果需要，则可使该纯化的水流661的一部分与来自该酸-水汽提器的NH3及H2S的气流662返回接触。在这种情况下，该NH3和H2S返回溶解在该部分液态水流661中，形成(NH4)2S，且随后将该溶液引入氧化反应器640，以便转化成(NH4)2SO4。然而，优选不使该纯化的水流与气流662返回接触且优选根据需要将物流662冷却，以使得在该物流中的水冷凝且在该物流中的NH3和H2S回到溶液中，形成(NH4)2S，且随后将该溶液引入氧化反应器640中，以便转化成(NH4)2SO4。该方法使得可以得到纯化的水流661且在氧化反应器540的出口处产生水、NH3和(NH4)2SO4的浓缩的处理流642。也将来自H2S去除单元的回收的H2S的物流652引入该氧化反应器中。
本发明方法的该第六实施方案使得可以得到纯化的水流661且在氧化反应器640的出口处产生水、NH3和(NH4)2SO4的浓缩的处理流642。其还提供冷却的蒸气产物的二次流651，二次流651可含有小浓度的H2S且促进H2S至(NH4)2SO4产物的高度总体转化。
已经发现由生物质(水陆基生物质、来自利用这些材料的工艺的废物)以及得自生物质或石油的塑料的加氢热解生成的炭是基本惰性的碳质材料，其不含对人类或植物有害的烃污染物。本发明的一个意图在于组合由生物质或塑料的加氢热解生成的炭与自该工艺回收的硫酸铵以生成作为粉末、颗粒状或粒化材料的农业肥料产物，该农业肥料产物可改善作为农业基材使用的土壤的品质以及提供用于供养木质纤维素生物质的施肥组分。
实施例
使具有代表大多数木材物类的性质的木材样品进行加氢热解。该木材的元素组成提供在下表A中。该组成在总体基础(包括在原料中的水分和灰分)和在无水无灰(MAF)的基础上提供。如在表A中可看出，在木材中存在少但显著量的氮和硫。
在离开实验性加氢热解器的蒸气流中获得的加氢热解产物的产率在表B中给出。在来自加氢热解器的蒸气流中最终并没有见到最初在该木材中存在的所有氮和硫。一些硫和一些氮在来自加氢热解器的固态产物(包括炭和灰分)的物流中以化学方式结合在一起。然而，该实验证明，在MAF基础上，在一次产物蒸气流中NH3的产量占原料质量的0.18%。在MAF基础上，H2S的产量构成原料质量的0.05%。应该注意到在表B中的总质量合计达104.83%。这是由于在加氢热解过程中给定量的无水无灰的木材与氢气反应，且所得产物具有比反应的木材更大的总质量。
例如，可以假定1千克的无水无灰的木材进行加氢热解。在这种情况下，蒸气流含有1.8克NH3和0.5克H2S。由于NH3和H2S的不同摩尔质量，这等同于0.106摩尔的NH3和0.014摩尔的H2S。NH3与H2S的摩尔比因此为7.4：1。为了在水溶液中形成(NH4)2S，对于每摩尔H2S需要两摩尔NH3。在离开加氢热解反应器的蒸气流中NH3和H2S的相对量大于使在该物流中的所有H2S与NH3反应的量，且生成(NH4)2S的水溶液。
另外，在加氢热解过程中与氢气的相互作用将在干燥无灰木材中的显著分数的氧转化成在离开加氢热解过程的蒸气流中的水蒸气。即使原料是完全干燥的，在木材原料的加氢热解期间仍然存在显著的水形成，且所生成的水的量足以将在加氢热解产物蒸气流中存在的所有NH3和H2S实质上且完全溶解。
虽然离开加氢热解反应器的所有或几乎所有的NH3最后都溶解于一次水流中，但H2S在水溶液中的溶解性取决于多种因素，诸如温度、压力和溶液的pH。NH3溶解于一次水流中将使溶液呈碱性，且这将显著增加H2S在该碱性水溶液中的溶解性。H2S和NH3在水溶液中自发地反应以形成(NH4)2S，尽管该硫化物可能以离解形式存在。然而，当将工艺蒸气冷却时，在产物蒸气流中的H2S不可能全部进入一次水流中。在实践中仍然不可能产生含有显著浓度的H2S的冷却的蒸气流。上述的本发明方法的各种实施方案提供该剩余浓度的H2S可从冷却的蒸气流中除去且最终与NH3和氧气反应以形成(NH4)2SO4的方法。
在实际实践中，传送到加氢该加氢热解器的生物质原料还将含有一定的水分，因此在来自该加氢热解器的加热的蒸气流中的实际量的水蒸气将比如果原料干燥的情况含有显著更多的水。该现象有助于从冷却的蒸气流中除去H2S，因为在一次水流中NH3和H2S的浓度将比如果原料完全干燥时它们的浓度更低，意思是更多的H2S可在如上所述本发明方法的实施方案的冷凝器和分离器中从冷却的蒸气流中汽提。(NH4)2S在水中的溶解性非常高，且含有高达52质量%的(NH4)2S的(NH4)2S溶液似乎是市售可得的。
表A.木材原料的组成
| 木材 | 初始组成 | 初始组成，MAF基础 |
| % C (MF) | 47.6 | 50.2 |
| % H (MF) | 5.7 | 6.0 |
| % O (MF) | 41.2 | 43.5 |
| % N (MF) | 0.2 | 0.2 |
| % S (MF) | 0.1 | 0.1 |
| %灰分(MF) | 1.1 | |
| %水分 | 4.3 |
表B.来自木材的加氢热解的热蒸气产物的在无水无灰(MAF)基础上产率
| 木材加氢热解热蒸气产物产率(MAF基础)： | 重量% |
| 汽油 | 16 |
| 柴油 | 10 |
| 炭 | 13 |
| 水 | 36 |
| CO | 8.4 |
| CO2 | 8.4 |
| C1-C3 | 12.8 |
| H2S | 0.05 |
| NH3 | 0.18 |
并不是所有的生物质都相同，且还试验了在机械性质、生长周期和组成方面与木材显著不同的第二原料。该原料为玉米秸。玉米秸包括在已经收获了植物的营养部分之后留下的玉米杆和皮的残余物。所检验的样品代表在收获玉米期间产生的大多数类型的玉米秸。玉米秸样品的组成在表C中在总体基础(包括在原料中的水分和灰分)上和在无水无灰(MAF)基础上提供。如在表C中可看出，正如木材原料的情况一样，在玉米秸中存在少但显著量的氮和硫。如从该表中可看出，玉米秸样品含有比木材样品多很多的灰分和多很多的水分。
与木材原料一样，在离开玉米秸加氢热解过程的热产物蒸气中硫化氢与氨的比率非常重要。在MAP基础上，发现玉米秸的加氢热解产物蒸气组成与木材的加氢热解产物蒸气组成非常类似。相关值示于表D中。在表B与表D之间的一个显著不同与在产物蒸气中的NH3和H2S的浓度有关。在玉米秸的情况下，在产物蒸气中NH3与H2S的摩尔比为15.2。此外，存在更加充足的NH3以与在产物蒸气流中的H2S反应并形成硫化铵。正如木材的情况，在玉米秸的加氢热解期间存在更加充足的所形成的水以将任何硫化铵完全溶解，且经过本发明的方法将载在溶液中。应该注意到在表D中的总质量合计达106%。这是由于在加氢热解过程中给定量的无水无灰的玉米秸与氢气反应，且所得产物具有比反应的原料更大的总质量。
表C.典型玉米秸样品的组成
| 玉米秸 | 初始组成 | 初始组成，MAF基础 |
| % C (MF) | 38.0 | 50.7 |
| % H (MF) | 4.8 | 6.4 |
| % O (MF) | 31.2 | 41.6 |
| % N (MF) | 0.9 | 1.2 |
| % S (MF) | 0.1 | 0.2 |
| %灰分(MF) | 8.3 | |
| %水分 | 20.0 |
表D.在MAF基础上典型玉米秸的加氢热解的流出蒸气的组成
| 玉米秸加氢热解热蒸气产物产率(MAF基础) | 重量% |
| 汽油 | 15 |
| 柴油 | 9 |
| 炭 | 15 |
| 水 | 36 |
| CO | 8.4 |
| CO2 | 8.4 |
| C1-C3 | 13.8 |
| H2S | 0.12 |
| NH3 | 0.92 |
虽然在上述说明书中已经关于某些优选的实施方案描述了本发明，且许多细节是出于说明的目的而陈述，但本发明的技术人员将显而易见本发明对另外的实施方案敏感且在本文中描述的某些细节可在不脱离本发明的基本原则的情况下显著改变。
本发明提供以下技术方案：
1.将生物质加工成烃燃料的方法，其包括：
在加氢热解反应器中加工生物质以产生烃燃料、炭和工艺蒸气流；
将所述工艺蒸气流冷却到产生水流的冷凝温度；
将所述水流送到催化反应器；
将空气注入所述催化反应器中以获得含有氨和硫酸铵的含水产物流；和
获得含有包含H2、CH4、CO、CO2、氨和硫化氢的不可凝工艺蒸气的冷却的产物蒸气流。
2.根据技术方案1的方法，其还包括：
维持所述水流处于约9-12的pH和对于在所述水流中送到所述催化反应器的每个硫原子具有5个氧原子的比率下。
3.根据技术方案1的方法，其还包括：
从所述冷却的产物蒸气流中除去硫化氢。
4.根据技术方案3的方法，其还包括：
将所述硫化氢与一次水流一起送到所述催化反应器以与在所述一次水流中存在的氨反应，从而形成硫化铵且随后形成硫酸铵；和
回收所述冷却的产物蒸气流产生硫化氢到硫酸铵的高总体转化率。
5.根据技术方案1的方法，其还包括：
用酸水汽提器处理离开所述催化反应器的水流，产生主要包含氨的气流和主要包含水和硫酸铵的水流。
6.根据技术方案5的方法，其中所述酸水汽提器安置在所述催化反应器上游。
7.根据技术方案1的方法，其还包括：
用酸水汽提器处理所述水流，产生纯化的液态水流和主要包含氨和硫化氢的气流；
将所述纯化的液态水与所述氨和硫化氢重新组合，以便在所述催化反应器中随后处理并转化。
8.根据技术方案1的方法，其还包括：
用安置在所述催化反应器上游的酸水汽提器处理所述水流；
从所述水流中除去所述硫化氢，产生几乎不含至不含硫化氢的冷却的工艺蒸气流，和纯化的水流。
9.根据技术方案1的方法，其还包括：
组合由所述生物质的加氢热解生成的炭与回收的硫酸铵以产生也为土壤改良剂的用于木质纤维素生物质的营养素。
10.根据技术方案9的方法，其还包括：
将炭和回收的硫酸铵的混合物粒化以产生也为土壤改良剂的用于木质纤维素生物质的强化营养素。
11.根据技术方案9的方法，其还包括：
将炭、回收的硫酸铵和农业肥料的混合物粒化以产生也为土壤改良剂的用于滋养木质纤维素生物质的强化营养素。
12.从生物质转化产物中除去硫的方法，其包括：
在加氢热解反应器中加工所述生物质，产生炭和含有氢气、水蒸气、可凝烃蒸气、不可凝烃蒸气、一氧化碳和二氧化碳的加热的工艺蒸气流；
将所述工艺蒸气流冷却到冷凝温度，产生冷却并冷凝的产物流；
将所述冷却并冷凝的产物流分离成气态组分和液态组分；
获得液态烃流；
获得含有水、氨和硫化铵的水流；
获得含有包含H2、CH4、CO、CO2、氨和硫化氢的不可凝工艺蒸气的冷却的产物蒸气流；
将所述水流送到催化反应器；
将空气注入所述催化反应器中，由此经催化剂氧化硫化铵，产生硫酸铵；
获得含有水、氨和硫酸铵的含水产物流；
从含有硫酸铵的所述含水产物流中蒸发过量的水，产生蒸汽和硫酸铵浓缩物；
冷却所述硫酸铵浓缩物以沉淀出作为结晶的硫酸铵的所述硫酸铵；和
滤出所述结晶的硫酸铵。
13.根据技术方案12的方法，其还包括以下步骤：
从含有水、氨和硫酸铵的所述水流汽提氨以产生气态氨的单独的纯化流。
14.根据技术方案13的方法，其还包括以下步骤：
将含有硫酸铵的所述水流引入锅炉中以将硫酸铵转化成结晶的硫酸铵和蒸汽。
15.根据技术方案12的方法，其还包括以下步骤：
将来自所述蒸发步骤的蒸汽送过保护床以从所述蒸汽中除去痕量的H2S。
16.根据技术方案15的方法，其还包括以下步骤：
将通过所述保护床的所述蒸汽送到蒸汽重整器。
17.根据技术方案14的方法，其还包括以下步骤：
将由所述锅炉产生的蒸汽送过保护床以从所述蒸汽中除去痕量的H2S。
Claims (21)
1.加氢热解方法，其包括：
将生物质和氢气引入包含一个或多个反应器的加氢热解器；使生物质充分去氧以提供加氢热解器的蒸气产物，其包含处于气态的去氧可凝烃、不可凝气体和水；
冷却蒸气产物以冷凝液态有机相和液态水相，所述液态水相包含溶解在该液态水相中包括氨（NH3）的蒸气产物的至少一部分物质；和
从该液态有机相中相分离该液态水相，并从水相中获得气相NH3产物或氢氧化铵产物。
2.权利要求1的方法，其中该加氢热解器包含串联的多个反应器。
3.权利要求1的方法，其中溶解的NH3在水相中存在量超过在水相中与H2S反应以生成(NH4)2S所消耗的量。
4.权利要求3的方法，其中氢氧化铵产物是跟随使水相与氧进行催化反应以将(NH4)2S基本上氧化为(NH4)2SO4获得的。
5.权利要求1的方法，其还包括：
从冷凝的有机和水相中分离包含包括不可凝烃和H2S的不可凝气体的冷却的蒸气相。
6.权利要求5的方法，其还包括处理该冷却的蒸气相以基本除去H2S。
7.权利要求6的方法，其中所述处理包括将该冷却的蒸气相与吸附床或与液体洗涤接触。
8.权利要求5的方法，其还包括使至少一部分该冷却的蒸气相经受蒸汽重整以生成氢。
9.权利要求1的方法，其中该方法包括通过使该液态水相经受酸水汽提获得气相NH3产物。
10.权利要求9的方法，其中该气相NH3产物是在跟随使该液态水相与氧进行反应以将(NH4)2S基本上氧化为(NH4)2SO4，然后使该液态水相经受酸水汽提获得的。
11.权利要求10的方法，其中使该液态水相与氧进行反应是催化进行的。
12.权利要求1的方法，其中氢氧化铵产物是跟随使该液态水相与氧进行反应以将(NH4)2S基本上氧化为(NH4)2SO4获得的。
13.权利要求1的方法，其中该生物质包含贡献给该液态水相的水分。
14.权利要求1的方法，其中该去氧可凝烃在液态有机相中基本被回收，并包含具有性质与汽油、柴油和煤油相应的烃。
15.权利要求1的方法，其中该生物质包含氮(N)和硫(S)，其量足以在该蒸气产物中形成NH3和H2S两者，NH3的量超过与H2S反应以生成(NH4)2S所需的量。
16.权利要求1的方法，其中液态水相包含比足以将最初在该蒸气产物中存在的NH3和H2S反应生成的(NH4)2S溶解更多的水。
17.用于制备氨产物的方法，其包括：
在加氢热解器中加工生物质，产生固态炭和含有氢、一氧化碳、二氧化碳、去氧可凝烃和水蒸气的加热的蒸气产物；
冷却该加热的蒸气产物以冷凝，作为分离的液相，有机相和水相，所述水相包含由NH3从该加热的蒸气产物溶解入该水相形成的NH4OH；和
分离液相并从水相中获得作为气相NH3产物或作为NH4OH含水产物的氨产物。
18.权利要求17的方法，其中水相还包含(NH4)2S，其得自于NH3和H2S两者从该加热的蒸气产物溶解入该水相并且部分溶解的NH3和溶解的H2S反应。
19.权利要求17的方法，其中该加氢热解器包含串联的多个反应器。
20.权利要求17的方法，其中该氨产物是通过使水相经受酸水汽提获得的气相NH3产物。
21.权利要求17的方法，还包括：
从液相中分离包含不可凝烃的冷却的蒸气相；和
蒸汽重整至少一部分该不可凝烃以生成用于在加氢热解器中加工生物质的氢。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/196645 | 2011-08-02 | ||
| US13/196,645 US8859831B2 (en) | 2011-08-02 | 2011-08-02 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| CN201280048542.5A CN103842299B (zh) | 2011-08-02 | 2012-07-26 | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280048542.5A Division CN103842299B (zh) | 2011-08-02 | 2012-07-26 | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105107346A true CN105107346A (zh) | 2015-12-02 |
| CN105107346B CN105107346B (zh) | 2017-09-08 |
Family
ID=46690698
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510554096.0A Active CN105107346B (zh) | 2011-08-02 | 2012-07-26 | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 |
| CN201280048542.5A Active CN103842299B (zh) | 2011-08-02 | 2012-07-26 | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280048542.5A Active CN103842299B (zh) | 2011-08-02 | 2012-07-26 | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 |
Country Status (17)
| Country | Link |
|---|---|
| US (2) | US8859831B2 (zh) |
| EP (2) | EP2739571B1 (zh) |
| JP (2) | JP6077540B2 (zh) |
| KR (2) | KR102092527B1 (zh) |
| CN (2) | CN105107346B (zh) |
| AR (1) | AR087438A1 (zh) |
| AU (2) | AU2012290464B2 (zh) |
| BR (2) | BR112014002376B1 (zh) |
| CA (1) | CA2843419C (zh) |
| CL (1) | CL2014000261A1 (zh) |
| MX (2) | MX362663B (zh) |
| MY (2) | MY178021A (zh) |
| RU (2) | RU2018114265A (zh) |
| SA (1) | SA112330748B1 (zh) |
| UA (2) | UA121749C2 (zh) |
| WO (1) | WO2013019558A1 (zh) |
| ZA (2) | ZA201400959B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442383A (zh) * | 2020-11-13 | 2021-03-05 | 新奥科技发展有限公司 | 一种煤的预处理方法 |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8859831B2 (en) * | 2011-08-02 | 2014-10-14 | Gas Technology Institute | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| US9416321B2 (en) * | 2012-05-18 | 2016-08-16 | Uop Llc | Separation process with modified enhanced hot separator system |
| US20140037507A1 (en) * | 2012-07-31 | 2014-02-06 | Hsiao-Lun WANG | Organic compound pyrolysis flashover energy-saving regeneration treatment system |
| NL2013230B1 (en) * | 2014-07-21 | 2016-08-16 | Airpack Holding B V | Method for upgrading biogas and production of ammonium sulphate. |
| US10392566B2 (en) | 2015-04-27 | 2019-08-27 | Gas Technology Institute | Co-processing for control of hydropyrolysis processes and products thereof |
| AU2016359795B2 (en) * | 2015-11-23 | 2019-08-15 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass into a liquid hydrocarbon material |
| WO2017089312A1 (en) * | 2015-11-23 | 2017-06-01 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass into a liquid hydrocarbon material |
| US10264578B2 (en) * | 2017-01-31 | 2019-04-16 | Qualcomm Incorporated | Listen before transmit (LBT) communication channel for vehicle-to-vehicle communications |
| US10246330B2 (en) | 2017-04-13 | 2019-04-02 | Marsulex Environmental Technologies Corporation | Systems and processes for removing hydrogen sulfide from gas streams |
| US11383995B2 (en) * | 2018-03-28 | 2022-07-12 | Heartland Water Technology, Inc. | Apparatus and method for treating hydrogen sulfide and ammonia in wastewater streams |
| CN109502556B (zh) * | 2018-11-28 | 2022-01-14 | 昆明理工大学 | 一种载硫磺后催化剂回收单质硫并再生的方法及系统 |
| US11967745B2 (en) * | 2022-04-27 | 2024-04-23 | Saudi Arabian Oil Company | Co-production of hydrogen, carbon, and electricity with carbon dioxide capture |
| US20240101415A1 (en) * | 2022-09-28 | 2024-03-28 | Saudi Arabian Oil Company | Co-production of hydrogen, carbon, electricity, and carbon monoxide with carbon dioxide capture for refining of crude oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415431A (en) * | 1982-07-14 | 1983-11-15 | Cities Service Company | Integrated oxygasification and hydropyrolysis process for producing liquid and gaseous hydrocarbons |
| CN87104309A (zh) * | 1986-05-20 | 1988-03-02 | 煤气技术研究所 | 流化床中含碳固体粒子气化时除去硫化合物的方法 |
| EP0857509A1 (en) * | 1997-01-08 | 1998-08-12 | Colt Engineering Corporation | Process for scrubbing ammonia and hydrogen sulfide from a fluid acid stream |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1021254A (en) | 1974-10-22 | 1977-11-22 | Ortloff Corporation (The) | Natural gas processing |
| US4336125A (en) * | 1979-07-20 | 1982-06-22 | Institute Of Gas Technology | Production of synthetic hydrocarbon fuels from peat |
| US4690807A (en) * | 1985-08-15 | 1987-09-01 | General Electric Environmental Services, Inc. | Process for the simultaneous absorption of sulfur oxides and production of ammonium sulfate |
| US4765873A (en) * | 1985-12-06 | 1988-08-23 | The Dow Chemical Company | Continuous process for the removal of hydrogen sulfide from a gaseous stream |
| US4749555A (en) | 1986-10-02 | 1988-06-07 | Shell Oil Company | Process for the selective removal of hydrogen sulphide and carbonyl sulfide from light hydrocarbon gases containing carbon dioxide |
| US5427762A (en) * | 1987-05-27 | 1995-06-27 | Hydrocarb Corporation | Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol |
| US4854249A (en) | 1987-08-03 | 1989-08-08 | Institute Of Gas Technology | Two stage combustion |
| US4913802A (en) | 1989-05-08 | 1990-04-03 | Uop | Process for sweetening a sour hydrocarbon fraction |
| US4908122A (en) | 1989-05-08 | 1990-03-13 | Uop | Process for sweetening a sour hydrocarbon fraction |
| US5207927A (en) | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| US5470486A (en) | 1994-06-20 | 1995-11-28 | Uop | Conversion of water-soluble inorganic sulfide compounds in an aqueous stream |
| US5536385A (en) | 1995-03-03 | 1996-07-16 | Envirocorp Services & Technology, Inc. | Production and purification of contaminated effluent streams containing ammonium sulfate and ammonia |
| DE19731062C2 (de) * | 1997-07-19 | 2001-07-12 | Lurgi Lentjes Bischoff Gmbh | Verfahren zur Entfernung von sauren Gasen aus Rauchgasen, insbesondere aus Kraftwerksabgasen und Abgasen von Müllverbrennungsanlagen |
| US6017501A (en) * | 1997-12-26 | 2000-01-25 | Marathon Oil Company | Disposal of hydrogen sulfide gas by conversion to sulfate ions in an aqueous solution |
| NL1011490C2 (nl) | 1999-03-08 | 2000-09-12 | Paques Bio Syst Bv | Werkwijze voor het ontzwavelen van gassen. |
| US6797154B2 (en) * | 2001-12-17 | 2004-09-28 | Chevron U.S.A. Inc. | Hydrocracking process for the production of high quality distillates from heavy gas oils |
| US20080031809A1 (en) * | 2006-07-18 | 2008-02-07 | Norbeck Joseph M | Controlling the synthesis gas composition of a steam methane reformer |
| RU2261891C1 (ru) * | 2004-05-31 | 2005-10-10 | Институт химии и химической технологии СО РАН (ИХХТ СО РАН) | Способ получения жидких углеводородных смесей из твердого углеродсодержащего сырья |
| EP1852493A1 (en) * | 2006-05-05 | 2007-11-07 | BIOeCON International Holding N.V. | Hydrothermal treatment of carbon-based energy carrier material |
| US7258848B1 (en) | 2006-07-31 | 2007-08-21 | E. I. Du Pont De Nemours And Company | Process for scrubbing ammonia from acid gases comprising ammonia and hydrogen sulfide |
| US7960520B2 (en) | 2007-06-15 | 2011-06-14 | Uop Llc | Conversion of lignocellulosic biomass to chemicals and fuels |
| US8217210B2 (en) * | 2007-08-27 | 2012-07-10 | Purdue Research Foundation | Integrated gasification—pyrolysis process |
| WO2009029660A2 (en) * | 2007-08-27 | 2009-03-05 | Purdue Research Foundation | Novel process for producing liquid hydrocarbon by pyrolysis of biomass in presence of hydrogen from a carbon-free energy source |
| JP2009093779A (ja) | 2007-09-19 | 2009-04-30 | Sony Corp | コンテンツ再生装置及びコンテンツ再生方法 |
| US8353980B2 (en) * | 2008-12-05 | 2013-01-15 | Marsulex Environmental Technologies Corporation | Flue gas scrubbing apparatus and process |
| US8915981B2 (en) * | 2009-04-07 | 2014-12-23 | Gas Technology Institute | Method for producing methane from biomass |
| US8492600B2 (en) * | 2009-04-07 | 2013-07-23 | Gas Technology Institute | Hydropyrolysis of biomass for producing high quality fuels |
| US20100251600A1 (en) * | 2009-04-07 | 2010-10-07 | Gas Technology Institute | Hydropyrolysis of biomass for producing high quality liquid fuels |
| US8063258B2 (en) * | 2009-05-22 | 2011-11-22 | Kior Inc. | Catalytic hydropyrolysis of organophillic biomass |
| AU2010313862B2 (en) | 2009-10-27 | 2014-10-23 | Ignite Resources Pty Ltd | Methods for producing hydrocarbon products from bio-oils and/or coal -oils |
| US8383871B1 (en) * | 2010-09-03 | 2013-02-26 | Brian G. Sellars | Method of hydrogasification of biomass to methane with low depositable tars |
| US8859831B2 (en) * | 2011-08-02 | 2014-10-14 | Gas Technology Institute | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
-
2011
- 2011-08-02 US US13/196,645 patent/US8859831B2/en active Active
-
2012
- 2012-07-26 AU AU2012290464A patent/AU2012290464B2/en active Active
- 2012-07-26 MY MYPI2014700228A patent/MY178021A/en unknown
- 2012-07-26 BR BR112014002376-0A patent/BR112014002376B1/pt active IP Right Grant
- 2012-07-26 CN CN201510554096.0A patent/CN105107346B/zh active Active
- 2012-07-26 MY MYPI2020002472A patent/MY195613A/en unknown
- 2012-07-26 JP JP2014523979A patent/JP6077540B2/ja active Active
- 2012-07-26 RU RU2018114265A patent/RU2018114265A/ru not_active Application Discontinuation
- 2012-07-26 UA UAA201610071A patent/UA121749C2/uk unknown
- 2012-07-26 EP EP12748300.6A patent/EP2739571B1/en active Active
- 2012-07-26 EP EP22150181.0A patent/EP4005981A1/en active Pending
- 2012-07-26 RU RU2014107841A patent/RU2653841C2/ru not_active IP Right Cessation
- 2012-07-26 WO PCT/US2012/048345 patent/WO2013019558A1/en active Application Filing
- 2012-07-26 CN CN201280048542.5A patent/CN103842299B/zh active Active
- 2012-07-26 KR KR1020197005683A patent/KR102092527B1/ko active Active
- 2012-07-26 KR KR1020147005634A patent/KR101955177B1/ko active Active
- 2012-07-26 UA UAA201402083A patent/UA113740C2/uk unknown
- 2012-07-26 CA CA2843419A patent/CA2843419C/en active Active
- 2012-07-26 MX MX2014001200A patent/MX362663B/es active IP Right Grant
- 2012-07-26 BR BR122015017656-5A patent/BR122015017656B1/pt active IP Right Grant
- 2012-08-01 SA SA112330748A patent/SA112330748B1/ar unknown
- 2012-08-02 AR ARP120102830A patent/AR087438A1/es active IP Right Grant
-
2014
- 2014-01-29 MX MX2019001085A patent/MX2019001085A/es active IP Right Grant
- 2014-01-31 CL CL2014000261A patent/CL2014000261A1/es unknown
- 2014-02-07 ZA ZA2014/00959A patent/ZA201400959B/en unknown
- 2014-10-13 US US14/512,841 patent/US9593282B2/en active Active
-
2015
- 2015-02-25 ZA ZA2015/01289A patent/ZA201501289B/en unknown
-
2017
- 2017-01-12 JP JP2017003335A patent/JP6441389B2/ja active Active
- 2017-02-16 AU AU2017201034A patent/AU2017201034B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415431A (en) * | 1982-07-14 | 1983-11-15 | Cities Service Company | Integrated oxygasification and hydropyrolysis process for producing liquid and gaseous hydrocarbons |
| CN87104309A (zh) * | 1986-05-20 | 1988-03-02 | 煤气技术研究所 | 流化床中含碳固体粒子气化时除去硫化合物的方法 |
| EP0857509A1 (en) * | 1997-01-08 | 1998-08-12 | Colt Engineering Corporation | Process for scrubbing ammonia and hydrogen sulfide from a fluid acid stream |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442383A (zh) * | 2020-11-13 | 2021-03-05 | 新奥科技发展有限公司 | 一种煤的预处理方法 |
| CN112442383B (zh) * | 2020-11-13 | 2022-03-04 | 新奥科技发展有限公司 | 一种煤的预处理方法 |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105107346B (zh) | 从加氢热解产物蒸气中以硫酸铵形式除去硫化氢 | |
| JP2014529635A5 (zh) | ||
| BR112013020016B1 (pt) | método de purificação de um gás obtido por gaseificação | |
| CN108064221A (zh) | 用于生产有机尿素的方法和由其获得的有机尿素及aus32 | |
| US20110070144A1 (en) | Process for conversion of waste fluid streams from chemical processing plants to beneficiary agriculture products | |
| DE102011105972A1 (de) | Verfahren zur Herstellung von Methionin | |
| NZ620809B2 (en) | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors | |
| NZ716910B2 (en) | Hydropyrolysis process | |
| US11472924B2 (en) | Methods and systems to decarbonize natural gas using sulfur to produce hydrogen and polymers | |
| Leijenhorst | Pyrolysis of Agro‐Digestate: Nutrient Distribution | |
| DE102008007296A1 (de) | Düngemittel und Verfahren zu dessen Herstellung | |
| CN101817501A (zh) | 硫化氢分解循环制氢气的方法 | |
| BR102023023555A2 (pt) | Método para fabricar um produto fertilizante agrícola |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |