NZ620809B2 - Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors - Google Patents
Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors Download PDFInfo
- Publication number
- NZ620809B2 NZ620809B2 NZ620809A NZ62080912A NZ620809B2 NZ 620809 B2 NZ620809 B2 NZ 620809B2 NZ 620809 A NZ620809 A NZ 620809A NZ 62080912 A NZ62080912 A NZ 62080912A NZ 620809 B2 NZ620809 B2 NZ 620809B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- stream
- water
- ammonia
- ammonium sulfate
- aqueous
- Prior art date
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 50
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 50
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 67
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 30
- 239000002028 Biomass Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 230000003197 catalytic Effects 0.000 claims abstract description 18
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000008213 purified water Substances 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- UYJXRRSPUVSSMN-UHFFFAOYSA-P Ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- BIGPRXCJEDHCLP-UHFFFAOYSA-N Ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 150000004763 sulfides Chemical class 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 4
- 230000001590 oxidative Effects 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 3
- 239000012084 conversion product Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000015097 nutrients Nutrition 0.000 claims 3
- 125000004429 atoms Chemical group 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 238000005453 pelletization Methods 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 239000002364 soil amendment Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000002023 wood Substances 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 14
- 235000005822 corn Nutrition 0.000 description 14
- 235000005824 corn Nutrition 0.000 description 14
- 241000209149 Zea Species 0.000 description 13
- 239000010907 stover Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- -1 sulfide compounds Chemical class 0.000 description 3
- 241001508691 Martes zibellina Species 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002588 toxic Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 210000000988 Bone and Bones Anatomy 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 239000002574 poison Substances 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
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000758 substrate Substances 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
Classifications
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- 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
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- 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
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- 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
- 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
- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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
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- 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
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- 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
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- 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
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
-
- 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
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- 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
Abstract
Disclosed is a method for processing biomass into hydrocarbon fuels and removing hydrogen sulphide by reacting with ammonia to form ammonium sulfate, wherein the method comprises: (a) processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and a process vapour stream(110); (b) cooling the process vapour stream to a condensation temperature (120); (c) separating the process vapour stream into a primary cooled vapour product stream, a liquid hydrocarbon stream, and a primary aqueous stream (130); wherein the primary cooled vapour product stream comprises non-condensable process vapours, hydrogen, hydrogen sulfide; carbon monoxide, and carbon dioxide, the liquid hydrocarbon stream comprises condensable hydrocarbons, and the primary aqueous stream comprises water, ammonia, hydrogen sulfide and ammonium sulfide; (d) treating the primary aqueous stream with a sour water stripper; (e) concentrating the hydrogen sulfide and ammonia into a cooled process water stream, and a second purified water stream; (f) sending the cooled process water stream to a catalytic reactor (140); (g) injecting air into the catalytic reactor (141) to obtain a concentrated treated stream containing water, ammonia and ammonium sulfate.; and a second gaseous stream containing nitrogen and oxygen (142). 110); (b) cooling the process vapour stream to a condensation temperature (120); (c) separating the process vapour stream into a primary cooled vapour product stream, a liquid hydrocarbon stream, and a primary aqueous stream (130); wherein the primary cooled vapour product stream comprises non-condensable process vapours, hydrogen, hydrogen sulfide; carbon monoxide, and carbon dioxide, the liquid hydrocarbon stream comprises condensable hydrocarbons, and the primary aqueous stream comprises water, ammonia, hydrogen sulfide and ammonium sulfide; (d) treating the primary aqueous stream with a sour water stripper; (e) concentrating the hydrogen sulfide and ammonia into a cooled process water stream, and a second purified water stream; (f) sending the cooled process water stream to a catalytic reactor (140); (g) injecting air into the catalytic reactor (141) to obtain a concentrated treated stream containing water, ammonia and ammonium sulfate.; and a second gaseous stream containing nitrogen and oxygen (142).
Description
REMOVAL OF HYDROGEN SULFIDE AS AMMONIUM
SULFATE FROM HYDROPYROLYSIS T VAPORS
Field of the Invention
This invention relates to a process that removes hydrogen sulfide (H2S) from
product vapors exiting a yrolysis reactor via reaction with ammonia (NH3) to form
ammonium sulfide. In addition, the process converts en sulfide to ammonium sulfate.
Description of Related Art
The process of the present invention relates to removal of H28 from the
effluent vapors exiting a hydropyrolysis reactor. Hydropyrolysis reactors are known in the
art.
Commercially, HZS is commonly removed from vapor streams via the Claus
process, in a Claus plant. In the Claus Process, H2S is ed to form sulfur e (802)
and then the sulfur dioxide is reacted with more H2S to produce water (H20) and elemental
sulfur. The overall reaction is:
2HZS+02—>Sz+2H20
This process is nown, and has been widely applied in the refining and reforming of
petroleum products. However, the process is complex, and often es multiple reaction
' steps. Moreover, the process can be most efficiently applied to s containing 25% or
more of H28, on a molecular basis. If streams containing ammonia, as well as HZS are
processed in a Claus plant, the ammonia is oxidized along with the H28. This is not ble,
e a is a potentially-valuable reaction product of the hydropyrolysis process.
A significant portion of the product vapor stream from the yrolysis
r comprises water vapor and hydrocarbons with boiling points below 70 degrees
Fahrenheit, at atmospheric pressure. The product vapor from the hydropyrolysis reactor must
be cooled to ambient temperatures in order for liquid hydrocarbons to be recovered as a
separate product stream. When the product vapor stream is cooled, water vapor in the product
vapor stream condenses to form liquid water, and a significant fraction of any H28 and any
NH3 in the product vapor stream go into solution in the liquid water. The resulting aqueous
solution then contains ammonia and e compounds.
Processes by which water-soluble sulfide compounds can be catalytically
reacted with oxygen to form stable sulfate compounds are disclosed in Marinangeli et al.,
U.S. Patent 5,207,927 Gillespie, U.S. Patent 5,470,486. The approach taught by Marinangeli
WO 19558 PCT/U82012/048345
et al., involves passing an s stream containing both the sulfide compound and oxygen
over an appropriate oxidizing catalyst, under conditions wherein the pH of the solution is 9—
12, and an oxygen-to—sulfur ratio greater than about 5 is maintained. The approach taught by
Gillespie requires a pH greater than 12 and an -to-sulfur ratio greater than about 4 be
maintained. Both approaches prefer metal phthalocynanines with Gillespie preferring the use
of carbon supports. A product stream that is substantially free of sulfide compounds is thus
obtained, since all sulfide nds have been converted to sulfate compounds.
SUMMARY OF THE INVENTION
In the hydropyrolysis r ofthe s of the present invention, a biomass
feedstock is ted into a stream containing the following:
1. Deoxygenated condensable hydrocarbons (with properties corresponding to those
of gasoline, diesel and kerosene)
2. ndensable hydrocarbon vapors (such as methane, ethane, e and
),
3. Other non—condensable vapors (C02, CO, and hydrogen),
4. Water and species which are soluble in liquid water, such as ammonia (NHg), and
hydrogen sulfide (H28).
The NH3 is present in the hydropyrolysis product stream due to the presence
of nitrogen in the biomass feedstock. The H28 is present in the hydropyrolysis stream due to
the presence of sulfur in the s feedstock. The nitrogen and the sulfur in the feedstock
react with hydrogen in the hydropyrolysis reactor to form NH3 and H28, respectively.
It is one object of this invention to provide a method by which hydrogen
sulfide can be removed from a product vapor stream, produced by the hydropyrolysis of
biomass. Hydropyrolysis experiments, in the course of which biomass was deoxygenated and
converted to products including hydrocarbons, have shown that the stream of vapor leaving
the hydropyrolizer contains water vapor, NH3, and H28, in proportions that make this product
uniquely suited to a process in which the H28 is combined with the NH3 in an aqueous
solution, and then oxidized to form ammonium sulfate. These experiments are original, and
the concentrations of nitrogen and sulfur compounds in the vapor stream are unexpected and
surprising. The experiments are described in detail in the examples presented below.
In order to carry out yrolysis in the hydropyrolysis reactor associated
with the present invention, some portion of the hydropyrolysis t stream from the
reactor may be sent to a steam reformer, and there d with steam to produce hydrogen.
Generally, it will be desirable to send some or all of the ndensable hydrocarbon
vapors, such as methane, ethane, butane, etc., to the reformer. The hydrogen thus obtained
may then be introduced back into the hydropyrolysis reactor, so that hydropyrolysis can
continue to be carried out. The need for a source of hydrogen, external to the yrolysis
process associated with the present ion, may thus be reduced or eliminated. Note that
H28 will be present in the t vapor stream from the hydropyrolysis process whenever
sulfiir is present in the feedstock, and the presence of the H28 creates several ms.
The H28 in the product vapor stream is highly toxic to humans. In addition, the
H2S can poison the catalysts ed in steam reforming of product vapors from the
hydropyrolysis reactor. er, the H28 can be reacted with NH3 to e ammonium
sulfide ((NH4)2S), and then oxidized to produce ammonium sulfate ((NH4)2SO4), a product
with considerable commercial value as a fertilizer.
The present invention describes a process which allows the H23 and NH3
contained in product vapor from hydropyrolysis of biomass to be captured in an aqueous
stream. Biomass hydropyrolysis experiments have demonstrated that the hydropyrolysis
process ated with the present invention produces a product stream that ns water
vapor, H28, and NH3 in particular quantities that make it possible to obtain the requisite
conditions for H2S removal via conversion to (NH4)2SO4. Substantially all the H28 captured
in the aqueous stream is reacted with NH3 to form (NH4)2S. In addition, a surplus of
unreacted NH3 is provided and dissolved in the aqueous stream, in order to increase the pH of
the aqueous stream to approximately 12 or greater or lesser as required for subsequent
conversion of (NH4)2S to (NH4)2SO4. The stream can then be reacted with oxygen in a
thermal, non-catalytic conversion zone to substantially convert the dissolved (NH4)2S to
(NH4)2SO4 and thiosulfate. The stream can be further contacted with oxygen and an
oxidizing catalyst in ance with the method disclosed in Gillespie, US. Patent
,470,486 or, alternatively, the incoming aqueous stream can be reacted with oxygen, in the
presence of an appropriate catalyst, in accordance with the method disclosed in the US.
Patent 927 (Marinangeli, et al.). By employing either technology, within the ranges of
pH, oxygen to sulfur mole ratio, pressure, temperature, and liquid hourly space velocities
In one aspect there is provided a method for processing biomass into hydrocarbon fuels
comprising:
processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and
a process vapor stream;
cooling the process vapor stream to a condensation temperature resulting in an aqueous
stream;
sending the aqueous stream to a catalytic reactor;
injecting air into the catalytic reactor to obtain an aqueous product stream containing
ammonia and ammonium sulfate; and
ing a cooled product vapor , containing non-condensable process vapors
comprising H2, CH4, CO, CO2, ammonia and hydrogen e.
In another aspect there is ed a method for removal of sulfur from biomass conversion
products comprising:
processing the biomass in a hydropyrolysis reactor, resulting in char and a heated process
vapor stream containing hydrogen, water vapor, condensable hydrocarbon vapors, noncondensable
hydrocarbon vapors, carbon monoxide and carbon dioxide;
g the process vapor stream to a condensation temperature to a cooled and condensed
product ;
AH26(10987121_1):RTK
separating the cooled and condensed product stream into a gaseous and liquid component;
obtaining a liquid hydrocarbon stream;
obtaining an aqueous , containing water, ammonia, and ammonium sulfide;
obtaining a cooled product vapor stream, containing non-condensable process vapors
comprising H2, CH4, CO, CO2, ammonia and hydrogen sulfide;
sending the aqueous stream to a tic reactor;
injecting air into the catalytic reactor thereby oxidizing ammonium sulfide over a catalyst
resulting in ammonium sulfate;
obtaining an aqueous product stream ning water, ammonia and ammonium e;
ating excess water from the aqueous t stream containing ammonium sulfate
resulting in steam and a concentrate of ammonium sulfate;
cooling the concentrate of ammonium sulfate to precipitate out the ammonium sulfate as
crystallized um sulfate; and
filtering out the crystallized ammonium sulfate.
AH26(10987121_1):RTK
WO 19558
shows a process flow diagram according to one preferred embodiment
of this invention, in which the treated s product stream, containing water, NH3, and
(NH4)2SO4, is treated in a sour-gas stripper.
shows a process flow diagram according to one preferred embodiment
of this invention, in which a sour-water stripper removes NH3 and H28 from the primary
s stream prior to the introduction of the s stream to the oxidation reactor.
shows a process flow diagram according to one preferred embodiment
of this invention, which incorporates both an H2S removal unit, associated with the cooled
vapor product stream, and a sour-water stripper upstream of the oxidation reactor.
DETAILED PTION OF THE PRESENTLY PREFERRED EMBODIMENTS
FIGS. 1-6 show various preferred embodiments of the t invention. shows a process flow diagram, illustrating the simplest embodiment of the s of the
present invention, in which H2S is captured in a primary aqueous stream containing NH3, and
oxidized in a reactor to form (NH4)2SOA. Product streams in this embodiment include a
cooled vapor stream comprising primarily process vapors, and ning some H2S, a liquid
stream comprising primarily condensed hydrocarbons, a second vapor stream comprising
primarily nitrogen and oxygen, and a treated aqueous stream comprising primarily water,
NH3, and (NH4)2SO4.
shows the first and most elementary embodiment of the process of the
present invention. Biomass 111 and hydrogen 112 are'introduced into a yrolizer 110,
which produces a solid, carbonaceous product 113 red to as char) and a product vapor
stream 114. The solid product 113 comprises primarily aceous residue, remaining after
the hydropyrolysis of the biomass feedstock 111. The product vapor stream 114 leaves the
hydropyrolizer 110 (which may comprise a single r, or multiple reactors in series) at a
temperature that is teristic of such hydropyrolytic processes, at a minimum, high
enough that all constituents are maintained in a gaseous state. However, as is characteristic of
such hydropyrolytic conversion processes, the temperature may also be cantly higher
than this minimum. The product vapor stream 114 primarily comprises:
1. Deoxygenated sable hydrocarbons (with properties corresponding to those
of gasoline, diesel and kerosene)
2. Non-condensable hydrocarbon vapors (such as methane, ethane, e and
butane),
3. Other ndensable vapors (CO2, CO, and H2),
4. Water and species which are soluble in liquid water, such as ammonia (NH3), and
hydrogen sulfide (H2S).
The vapor stream is passed through a condenser 120, or other device, or other
set of devices, wherein the temperature of the vapor stream is reduced to a point where
substantially all the condensable hydrocarbons can be recovered as a liquid stream. At this
point, three phases develop: A cooled vapor phase, a hydrocarbon phase, and an aqueous
phase. The cooled product stream, containing all three phases, is sent to a separator 130,
where the three phases can be split up into three separate streams.
The sable hydrocarbon product stream 132 is preferably recovered at
this point. The H2S that was initially in the hot product vapor stream 114 is now divided, with
some exiting the separator in the cooled vapor stream 131, and some in the primary aqueous
stream 133. A trace of H28 may also-be present in the liquid hydrocarbon stream 132, but the
solubility of the polar H2S molecule in the liquid hydrocarbon stream is minimal.
The cooled vapor product stream 131 leaving the separator comprises
ily H2, ndensable hydrocarbons, CO2, CO, and H28.
The primary aqueous stream 133 leaving the separator comprises primarily
water, NH3, and ammonium sulfide ((NH4)2S). The (NH4)2S in this stream is ed when
the H28 from the vapor stream enters the aqueous stream and reacts with NH3, which is also
in solution in the aqueous stream. It is an object of this invention to control the process of the
invention in such a manner that the pH of the primary aqueous stream 133 is approximately
12, meaning that the concentration of NH3 (as NH4OH) in the stream is great enough to
produce a strongly—basic solution. This is helpful, in part, to help stabilize the H28 and
increase its solubility in the s stream. It is also a preferred condition for the operation
of the ion reactor 140, wherein the (NH4)2S is oxidized to produce (NH4)2SO4.
The primary aqueous stream 133 from the separator 130 is then introduced to
an oxidation reactor 140, also referred to as a catalytic reactor herein. A stream of air 141 is
also introduced to the ion r, in an amount sufficient to supply approximately 5
moles of oxygen for each mole of sulfur. After reaction at an appropriate temperature and
pressure, in the presence of an appropriate catalyst, and for a sufficient residence time, the
(NH4)2S in the primary aqueous stream 133 is substantially completely oxidized.
In accordance with this first embodiment of the process of the present
invention, a treated aqueous product stream 142 is preferably obtained from the oxidation
r, including NH3, liquid water, and (NH4)2SO4. In addition, a reactor gas product stream
143 is obtained from the oxidation reactor, primarily comprising nitrogen and unused oxygen,
and containing traces of NH3 and water vapor. It will be noted that, in this first embodiment,
a significant concentration of H28 is still present in the cooled product vapor stream 131
g the separator unit 130.
is a process flow diagram, illustrating an embodiment of the s of
the present ion, in which H2S that still remains in the cooled vapor product stream is
captured in a sorbent bed. In this case, removal of the H28 remaining in the cooled product
vapor stream is ntially te.
illustrates a second embodiment of the process of the present invention.
In this second embodiment an H28 removal unit 250 has been added, ream of the
separator 230. The y cooled vapor product stream 231 passes h the H28 removal
unit 250 (which may comprise a sorbent bed, liquid wash, or other similar apparatus). The
H28 in the y cooled vapor product stream 231 is substantially completely removed
from the primary cooled vapor product stream 231, and a secondary cooled vapor product
stream 251 comprising primarily H2, C0, C02, and non-condensable hydrocarbon vapors is
obtained. In this embodiment, the H28 is not recovered, and would, for example, be disposed
of when the H28 removal unit 250 is regenerated with H2S-containing waste being
appropriately discarded.
illustrates a third embodiment of the process of the present invention.
In this third embodiment, an H2S removal unit 350 has been added, ream of the
separator 330, as in the second embodiment, described above. The primary cooled vapor
product stream 331 passes through the H28 removal unit 350 (which may comprise a reusable
sorbent bed, amine scrubber, or some similar apparatus). The H28 in the primary cooled
vapor product stream 331 is substantially tely removed, and a secondary cooled vapor
t stream 351 comprising primarily H2, C0, C02, and non-condensable hydrocarbon
vapors is obtained. However, in this third embodiment, the H28 is recovered from the H28
removal unit 350, in a stream 352 comprising primarily gaseous H28, and is sent to the
oxidation reactor 340, along with the y aqueous stream 333. In the ion reactor,
the gaseous H28 stream 352 is brought into contact with the primary aqueous stream 333 and
an appropriate catalyst, and forms (NH4)2S, which is then oxidized to form (NH4)2SO4. In this
way, a secondary cooled product vapor stream 351, containing only trace s of H28,
and comprising ily H2, non-condensable hydrocarbons, CO2, and CO, is obtained. In
on, the overall conversion of H28 is increased, and is higher than in the first
embodiment of the process of the present invention, described above.
illustrates a fourth embodiment of the process of the present invention.
Ammonia (NH3) is a potentially-valuable product, and is separated from the primary treated
aqueous stream 442 leaving the oxidation reactor 440 in a ater stripper 460 in this
fourth embodiment of the process of the present invention. This ch allows a gaseous
stream 461 comprising primarily NH3 to be recovered, while the water and (NH4)2SO4 are
recovered separately from the ater stripper in a secondary treated aqueous stream 462.
(NH4)2$O4 is highly water-soluble, and the aqueous solution of (NH4)2SO4 has potential
value as an agricultural fertilizer. If desired, this solution can be concentrated by further
heating of the secondary treated aqueous stream 462, which could drive off some or all of the
water in the stream.
illustrates a fifth embodiment of the process of the present invention.
This embodiment features a sour-water stripper 560 upstream of the oxidation r 540,
2O which accepts the primary aqueous stream 533 from the tor. Water, NH3 and H28, and
any (NH4)2S formed by the reaction of NH3 and H28, are removed in the sour-water stripper
560, and leave the sour—water stripper as a gaseous stream 562. A stream of purified liquid
water 561 is thereby produced. This purified water stream 561 is then available as a product
stream. If desired, a portion of this purified water stream 561 can be brought back into
contact with the gaseous stream 562 of NH3 and H28 from the sour-water stripper. In this
case, the NH3 and H28 go back into solution in this portion of the liquid water stream 561,
forming (NH4)2S, and this solution is then introduced into the oxidation reactor 540, for
conversion to '(NH4)2SO4. However, preferably the purified water stream is not brought back
into contact with the gaseous stream 562 and preferably, stream 562 is cooled as needed so
that water in the stream is condensed and the NH3 and H28 in this stream go back into
solution g S, and this solution is then introduced into the oxidation reactor 540,
for conversion to (NH4)2SO4. This approach makes a stream of purified water 561 available,
and creates a concentrated treated stream 542 of water, NH3 and (NH4)2SO4 at the outlet of
the oxidation reactor 540.
illustrates a‘sixth embodiment of the process of the present invention.
This embodiment features a sour-water stripper 660 upstream of the oxidation reactor 640,
which accepts the primary aqueous stream 633 from the separator 630. It also features an H2S
removal unit 650 ream of the separator 630, as in the third embodiment described
herein above. The primary cooled vapor product stream 631 passes through the H28 removal
unit 650 (which may comprise a sorbent bed, amine scrubber, or some similar apparatus).
The H28 in the y cooled vapor t stream 631 is ntially completely removed
and a secondary cooled product vapor stream 651 comprising primarily H2, C0, C02, and
non-condensable hydrocarbon vapors is obtained. As in the third embodiment, the H28 is
recovered, in a stream 652 comprising primarily gaseous H2S, and is sent to the oxidation
reactor 640.
As described herein above in the description of the fifth embodiment,
dissolved NH3 and H28, and any (NH4)2S formed by the reaction ofNH3 and H28, are driven
out of the primary aqueous stream 633 in the ater stripper 660. Water, NH; and H28,
and any $ formed by the reaction of NH3 and H28, are removed in the sour-water
stripper 660, and leave the sour-water er as a gaseous stream 662. A stream of purified
water 661 is thereby produced. This purified water stream‘66l is then available as a t
stream. If desired, a portion of this purified water stream 661 can be brought back into
contact with the gaseous stream 662 of NH3 and H28 from the sour—water er. In this
case, the NH3 and H28 go back into solution in this portion of the liquid water stream 661,
forming S, and this solution is then introduced into the oxidation reactor 640, for
conversion to (NH4)2SO4. However, preferably the purified water stream is not brought back
into contact with the gaseous stream 662 and preferably, stream 662 is cooled as needed so
that water in the stream is sed and the NH3 and H28 in this stream go back into
solution forming (NH4)2S, and this solution is then introduced into the oxidation reactor 640,
for sion to (NH4)2SO4. This approach makes a stream of purified water 661 available,
and creates a concentrated treated stream 642 of water, NH3 and (NH4)2SO4 at the outlet of
the oxidation reactor 540. The stream 652 of recovered H2S from the H28 l unit is also
introduced to the oxidation reactor.
This sixth embodiment of the process of the present invention makes a stream of
purified water 661 available, and creates a concentrated treated stream 642 of water, NH3 and
(NH4)ZSO4 at the outlet of the oxidation reactor 640. It also es a secondary stream of
cooled vapor t 651 which may contain minute concentrations of H28, and promotes
high overall sion of H28 to an (NH4)2SO4 product.
The char produced from the hydropyrolysis of biomass (land and water based
biomass, wastes from processes utilizing these materials), as well as plastics derived from
biomass or petroleum has been found to be an essentially inert carbonaceous material, free of
hydrocarbon contaminants that are toxic to humans or plants. It is one intent of this invention
to combine the char produced from the yrolysis of biomass or plastic with the
ammonium sulfate recovered from this process to produce an agricultural fertilizer product,
as a powder, granulated, or pelletized material that can both improve the y of a soil for
use as an agricultural substrate and provide a fertilizing component for the sustenance of
lignocellulosic biomass.
EXAMPLES
A sample of wood with properties representative of those of most wood
species was ted to hydropyrolysis. The tal composition of the wood is presented
in Table A, below. The composition is presented on both an overall basis (which includes
moisture and ash in the feedstock) and on a moisture- and ash-free (MAF) basis. As can be
seen in Table A, small but significant quantities of nitrogen and sulfiir were t in the
wood.
The yield of hydropyrolysis products, obtained in the vapor stream leaving the
experimental hydropyrolizer, is given in Table B. Not all of the nitrogen and sulfur initially
present in the wood is ultimately found in the vapor stream from the hydropyrolizer. Some of
the sulfur and some of the nitrogen are chemically bound up in the stream of solid product
(comprising char and ash) from the hydropyrolizer. However, the experiment demonstrated
that the yield of NH3 in the primary product vapor stream tuted 0.18% of the mass of
the ock, on an MAF basis. The yield of H28 constituted 0.05% of the mass of the
feedstock, on an MAF basis. It will be noted that the total masses in Table B add up to
104.83%. This is due to the fact that a given quantity of moisture and ash-free wood reacts
with hydrogen in the hydropyrolysis process, and the resulting ts have a r total
mass than the wood that was reacted.
2012/048345
As an example, one might assume that one kilogram of moisture-free, ash-free
wood is subjected to hydropyrolysis. In this case, the vapor stream contains 1.8 grams ofNH3
and 0.5 grams of H28. Due to the different molar masses of NH3 and H28, this equates to
0.106 moles of NH3 and 0.014 moles of H28. The molar ratio of NH3 to H2S is therefore 7.4
to 1. In order to form (NH4)2S in an aqueous solution, two moles ofNH3 are required for each
mole of H28. The ve amounts of NH; and H28 in the vapor stream leaving the
hydropyrolysis reactor are more than te to react all the H2S in the stream with NH3,
and produce an aqueous solution of (NH4)28.
Further, the interaction with hydrogen in the hydropyrolysis process converts a
significant on of the oxygen in the dry, ee wood into water vapor in the vapor
stream leaving the hydropyrolysis s. Even if the feedstock is completely dry, there is
still a significant formation of water during hydropyrolysis of the wood feedstock, and the
amount of water produced is ent to substantially and completely dissolve all of the NH3
and H28 present in the hydropyrolysis product vapor stream.
While all or almost all of the NH; leaving the hydropyrolysis reactor
ultimately goes into solution in the primary aqueous , the solubility of H28 in aqueous
solutions s on a variety of factors, such as temperature, pressure, and pH of the
solution. The NH3 in solution in the primary aqueous stream will render the solution alkaline,
and this will significantly increase the solubility of H28 in the alkaline aqueous solution. H28
and NH3 react spontaneously in aqueous solution to form (NH4)2S, though the sulfide may be
present in a dissociated form. r, not all the H28 in the product vapor stream is likely
to enter the primary aqueous stream when the process vapors are cooled. A cooled vapor
stream, containing a significant concentration of H28, is still likely to result in practice. The
various embodiments of the process of the present invention, described above, provide means
by which this ing tration of H28 can be removed from the cooled vapor stream,
and, ultimately, reacted with NH3 and oxygen to form (NH4)2SO4.
In actual practice, the biomass feedstock conveyed into the hydropyrolizer will
also contain some moisture, so the actual amount of water vapor in the heated vapor stream
from the hydropyrolizer will contain significantly'more water that would be the case if the
feedstock were bone dry. This phenomenon assists in removal of H28 from the cooled vapor
stream, since the concentrations ofNH; and H28 in the primary aqueous stream will be even
lower than they would be if the feedstock were completely dry, meaning that more H28 can
WO 19558
be stripped from the cooled vapor stream in the ser and separator of the embodiments
of the process of the present ion, described herein above. The solubility of (NH4)ZS in
water is very high, and solutions of (NH4)ZS containing up to 52% by mass of (NH4)2S appear
to be commercially ble.
Initial Composition
_—_!_
% moisture
Table A. Composition of Wood Feedstock
Wood yrolysis
Hot Vapor Product Yield
(MAF Basis):
Table B. Yield of hot vapor products from hydropyrolysis of wood,
on a moisture- and ash—free (MAF) basis
Not all biomass is equivalent, and a second ock, which differs
significantly from wood in terms of mechanical properties, growth cycle, and composition,
was also tested. This feedstock was com stover. Corn stover includes residues of corn stalks
and husks, left over after the nutritious parts of the plant have been harvested. The sample
examined was typical of most types of corn stover generated during harvesting of corn. The
composition of the corn stover sample is presented on both an overall basis (which includes
moisture and ash in the feedstock) and on a moisture- and ash—free (MAF) basis in Table C.
As can be seen in Table C, small but significant quantities of nitrogen and sulfur were present
in the corn stover, as was the case with the wood feedstock. As can be seen from the table,
the corn stover sample contained far more ash and far more moisture than did the sample of
wood.
As with the wood feedstock, the ratio between hydrogen sulfide and ammonia
in the hot product vapor leaving the corn stover hydropyrolysis process is very important.
The hydropyrolysis product vapor composition of corn stover was found to be very similar to
that of wood, on an MAF basis. The relevant values are shown in Table D. One significant
difference between Tables B and D relates to the trations of NH3 and H2S in the
product vapor. The molar ratio ofNH3 to H28 in the product vapor, in the case of corn stover,
is 15.2. Again, there is more than enough NH3 present to react with the H28 in the product
there is more than
vapor stream and form um sulfide. As was the case with wood,
sufficient water formed, during hydropyrolysis of corn stover, to completely dissolve any
um sulfide, and carry it in solution through the process of the present invention. It
will be noted that the total masses in Table D add up to 106%. This is due to the fact that a
given quantity of moisture and ash-free corn stover reacts with en in the
hydropyrolysis s, and the resulting products have a greater total mass than the
ock that was reacted.
Initial Composition Initial Composition, MAF Basis
% c (MF)
H( “—
% O (MF)
% N (MF)
% S (MF)
% ash (MF)
% moisture
Table C. Composition of corn typical stover sample
Corn Stover
Hydropyrolsyis Hot
Vapor Product Yield
(MAF Basis):
Table D. Composition of t vapor, hydropyrolysis of
typical corn stover, on MAF basis
While in the foregoing specification this invention has been described in
relation to certain preferred embodiments thereof, and many details have been set forth for
purpose of illustration, it will be nt to those skilled in the art that the invention is
susceptible to additional embodiments and that n of the details described herein can be
varied considerably without departing from the basic principles of the invention.
WE
Claims (22)
1. A method for processing biomass into hydrocarbon fuels sing: sing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and a process vapor stream; cooling the process vapor stream to a condensation temperature resulting in an aqueous stream; sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor to obtain an aqueous product stream containing ammonia and ammonium sulfate; and obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and en sulfide.
2. The method of claim 1 r comprising: maintaining the aqueous stream at a pH of approximately 9-12 and a ratio of 5 atoms of oxygen for each atom of sulfur sent to the catalytic reactor in the aqueous stream.
3. The method of claim 1 or claim 2 further comprising: removing hydrogen e from the cooled product vapor stream.
4. The method of claim 3 further comprising: sending the hydrogen sulfide to the catalytic r, along with the aqueous stream, to react with ammonia present in the aqueous , to form ammonium sulfide and then ammonium sulfate; and recovering the cooled product vapor stream resulting in a high overall conversion of hydrogen sulfide to ammonium sulfate.
5. The method of any one of claims 1 to 4, further comprising: treating the aqueous stream leaving the tic reactor with a sour water stripper resulting in a gaseous stream comprising primarily ammonia and an aqueous stream comprising ily water and ammonium sulfate.
6. The method of claim 5 wherein the sour water stripper is positioned upstream of the catalytic r. AH26(10987121_1):RTK
7. The method of any one of claims 1 to 6 further comprising: treating the aqueous stream with a sour water stripper resulting in a stream of purified liquid water and a gaseous stream comprising primarily ammonia and hydrogen sulfide; recombining the purified liquid water with the ammonia and hydrogen sulfide, for subsequent treatment and sion in the catalytic r.
8. The method of any one of claims 1 to 7 further comprising: treating the aqueous stream with a sour water stripper positioned upstream of the catalytic reactor; removing the hydrogen sulfide from the aqueous stream resulting in a cooled process vapor stream, containing little to no hydrogen sulfide, and a purified water stream.
9. The method of any one of claims 1 to 8 further comprising: combining char produced from the hydropyrolysis of the s with red ammonium sulfate to create a nutrient for lignocellulosic s that also is a soil amendment.
10. The method of claim 9 further comprising: pelletizing the mixture of char and recovered ammonium sulfate to create a densified nutrient for lignocellulosic biomass that also is a soil ent.
11. The method of claim 9 further comprising: pelletizing the mixture of char, recovered ammonium sulfate, and agricultural fertilizers to create a densified nutrient for nourishing ellulosic biomass that also is a soil ent.
12. A method for removal of sulfur from biomass conversion products sing: sing the biomass in a hydropyrolysis reactor, resulting in char and a heated process vapor stream containing hydrogen, water vapor, condensable hydrocarbon vapors, densable hydrocarbon vapors, carbon monoxide and carbon dioxide; cooling the process vapor stream to a sation temperature to a cooled and condensed product stream; separating the cooled and condensed product stream into a gaseous and liquid component; obtaining a liquid hydrocarbon stream; obtaining an aqueous stream, containing water, ammonia, and ammonium sulfide; obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and hydrogen sulfide; AH26(10987121_1):RTK sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor y oxidizing ammonium sulfide over a catalyst resulting in ammonium e; obtaining an aqueous product stream containing water, ammonia and ammonium e; evaporating excess water from the aqueous product stream containing ammonium sulfate resulting in steam and a concentrate of ammonium sulfate; cooling the concentrate of ammonium sulfate to precipitate out the ammonium sulfate as crystallized ammonium sulfate; and ing out the crystallized um sulfate.
13. The method of claim 12 further comprising the step of: stripping ammonia from the aqueous stream containing water, ammonia and ammonium sulfate to create a te purified stream of gaseous ammonia.
14. The method of claim 13 further comprising the step of: introducing the aqueous stream containing ammonium sulfate a boiler to convert ammonium e to crystallized ammonium sulfate and steam.
15. The method of any one of claims 12 to 14 further comprising the step of: sending the steam from the evaporation step through a guard bed to remove trace H2S from the steam.
16. The method of claim 15 r comprising the step of: g the steam passing from the guard bed to a steam reformer.
17. The method of claim 14 further comprising the step of: sending the steam created by the boiler through a guard bed to remove trace H2S from the steam.
18. The method of claim 17 further comprising the step of: sending the steam passing from the guard bed to a steam reformer.
19. The method of any one of claims 12 to 18 wherein the catalyst is monosulfonated cobalt phthalocynanine. AH26(10987121_1):RTK
20. A hydrocarbon fuel made by the method of claim 1.
21. A method for processing biomass into hydrocarbon fuels, said method being according to claim 1 and substantially as herein described with reference to any one of the es.
22. A method for processing biomass into hydrocarbon fuels, said method being according to claim 1 and substantially as herein described with reference to any one of the anying drawings. Gas Technology Institute By the Attorneys for the Applicant SPRUSON & FERGUSON Per: AH26(11370162_1):RTK
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ716910A NZ716910B2 (en) | 2011-08-02 | 2012-07-26 | Hydropyrolysis process |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/196,645 US8859831B2 (en) | 2011-08-02 | 2011-08-02 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
US13/196,645 | 2011-08-02 | ||
PCT/US2012/048345 WO2013019558A1 (en) | 2011-08-02 | 2012-07-26 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ620809A NZ620809A (en) | 2016-06-24 |
NZ620809B2 true NZ620809B2 (en) | 2016-09-27 |
Family
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