CN109153921A - The inner heat material combination hydrocarbon pyrolysis - Google Patents
The inner heat material combination hydrocarbon pyrolysis Download PDFInfo
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- CN109153921A CN109153921A CN201780028865.0A CN201780028865A CN109153921A CN 109153921 A CN109153921 A CN 109153921A CN 201780028865 A CN201780028865 A CN 201780028865A CN 109153921 A CN109153921 A CN 109153921A
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- hydrocarbon
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- hgm
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- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 152
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 146
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 146
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 87
- 238000007600 charging Methods 0.000 claims abstract description 76
- 238000005336 cracking Methods 0.000 claims abstract description 51
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 102
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 78
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011973 solid acid Substances 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 17
- 230000008016 vaporization Effects 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 238000009834 vaporization Methods 0.000 claims description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 12
- -1 ethylene, propylene, butylene, benzene Chemical class 0.000 claims description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 210000004556 brain Anatomy 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 21
- 230000007935 neutral effect Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 35
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 7
- 239000003915 liquefied petroleum gas Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000004002 naphthaldehydes Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
-
- 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
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Information Retrieval, Db Structures And Fs Structures Therefor (AREA)
Abstract
A method of cracking hydrocarbon charging comprising exothermic material (HGM) stream by hydrocarbon charging is vaporized and comprising at least one aldehydes or ketones is introduced into cracking reactor.The hydrocarbon charging and HGM stream are vaporized before or after being introduced into the cracking reactor and can be vaporized.The HGM is added to provided in endothermic cracking process be used to crack required heat and facilitate whole process realize it is neutral.The method includes cracking the hydrocarbon charging to generate pyrolysis product, wherein the pyrolysis product includes C1‑C4Hydrocarbon and C5+ hydrocarbon.
Description
Cross reference to related applications
It is described this application claims the equity for the U.S.Provisional Serial 62/335,187 that on May 12nd, 2016 submits
Application is incorporated herein by reference.
Technical field
Embodiment of the disclosure relates generally to the processing of hydrocarbon, and is split more particularly to a kind of with exothermic material combination hydrocarbon
The method of solution preocess cracking hydrocarbon charging.
Background technique
Energy consumption is the notable obstacle in light olefin industry.The hydrocarbon pyrolysis is a kind of highly endothermic process.During the hydrocarbon pyrolysis,
With the beginning of cracking reaction, the temperature of reactor shell declines, because the heat consumption of the starting of endothermic cracking process is than anti-
Device is answered to increase other heat faster.Increase other heat with keep temperature of reactor can dramatically increase the hydrocarbon pyrolysis operation at
This.For example, current steam-cracking process operates at 800-1000 DEG C, energy used in entire petrochemical industry is consumed up to
40%.For newest steam cracking, specific energy consumption is the ethylene of about 4500-5000kcal/kg.Generally speaking, it is typically based on
About 70% production cost is due to energy consumption in the olefin plants of ethane or naphtha.
Summary of the invention
In the above context, the cracked hydrocarbon feeder pathway of exploitation efficient and cost-effective is continuously needed to generate the petrochemical industry of high demand
Basic material (building block).
Embodiment of the disclosure is related to mentioning using heat release exothermic material (HGM) for the energy requirement for hydrocarbon pyrolysis process of absorbing heat
For the method for the cracking hydrocarbon charging of fuel.The cost of energy as needed for the traditionally hydrocarbon pyrolysis is high, disclosed method and
System is industrially applicable, specifically in oil and natural gas industry.Be not limited to theory, add the HGM of the disclosure with
Help hydrocarbon pyrolysis process becomes energy neutral or close to energy neutral, to reduce gross energy cost relevant to the hydrocarbon pyrolysis.
According to one embodiment, a kind of method for cracking hydrocarbon charging is provided.The method includes vaporization hydrocarbon charging and vapour
Change the exothermic material (HGM) comprising at least one aldehydes or ketones to flow.In addition, the method includes the hydrocarbon chargings that will be vaporized and vaporization
Heating material stream is introduced into cracking reactor.Finally, the method also includes cracking hydrocarbon charging to generate pyrolysis product, wherein splitting
Solving product includes C1-C4Hydrocarbon and C5+ hydrocarbon.Pyrolysis product may include ethylene, propylene, butylene, benzene,toluene,xylene, ethylo benzene,
H2, methane, ethane, LPG, naphtha, gasoline and gas oil.
According to another embodiment, the method for cracking hydrocarbon charging is provided.The method includes vaporization hydrocarbon charging and vaporizations
Exothermic material (HGM) stream comprising at least one aldehydes or ketones.In addition, the method includes the hydrocarbon chargings that will be vaporized and vaporization
HGM stream is heated at least 100 DEG C of pre-reaction temperature, and the hydrocarbon charging of vaporization and the heating material stream of vaporization are introduced cracking
In reactor.Finally, wherein pyrolysis product includes C the method also includes cracking hydrocarbon charging to generate pyrolysis product1-C4Hydrocarbon and
C5+ hydrocarbon.Pyrolysis product may include ethylene, propylene, butylene, benzene,toluene,xylene, ethylo benzene, H2, methane, ethane, LPG, stone brain
Oil, gasoline and gas oil.
According to still another embodiment, the method for cracking hydrocarbon charging is provided.The method includes by hydrocarbon charging and comprising
Exothermic material (HGM) stream of at least one aldehydes or ketones is introduced into cracking reactor.The method also includes in cracking reactor
Vaporize hydrocarbon charging and heating material stream.Finally, the method also includes cracking hydrocarbon charging to generate pyrolysis product, wherein cracking produces
Object includes C1-C4Hydrocarbon and C5+ hydrocarbon.Pyrolysis product may include ethylene, propylene, butylene, benzene,toluene,xylene, ethylo benzene, H2, first
Alkane, ethane, LPG, naphtha, gasoline and gas oil.
The other feature and advantage of described embodiment will illustrate in specific embodiment below, and ability
The technical staff in domain will partly be easily aware of from the description, or by practicing described embodiment (including hereafter
Specific embodiment, claim and attached drawing) and recognize.
It should be understood that aforementioned be generally described describes various embodiments with following specific embodiments, and it is intended to provide general
It states or frame is for understanding the property and feature of advocated theme.Including attached drawing to provide to the further of various embodiments
Understand, and the attached drawing is incorporated into this specification and forms part of this specification.In Detailed description of the invention embodiment
Described various embodiments, and together with the description for explaining the principle and operation of required theme.
Detailed description of the invention
Fig. 1 is that the laboratory scale reactor assembly according to one or more other embodiments of the present disclosure for operation shows
It is intended to.
Fig. 2 is the catalyst bed under 560 DEG C of reaction temperature in the case where existing and feeding there is no exothermic material
The temperature curve of temperature.
Fig. 3 is the catalyst bed under 584 DEG C of reaction temperature in the case where existing and feeding there is no exothermic material
The temperature curve of temperature.
Specific embodiment
Now with detailed reference to the embodiment for using the HGM of the disclosure to crack for improving hydrocarbon charging.As previously mentioned, hydrocarbon is split
Solution is a kind of endothermic process.By by the hydrocarbon pyrolysis reaction in conjunction with HGM, traditional endothermic cracking process can become it is neutral or
Close to neutral.When specifically, during including the hydrocarbon pyrolysis in the disclosure, HGM generates heat release.The heat release can provide
For the heat other needed for hydrocarbon pyrolysis process that absorbs heat.In addition, HGM is also used as diluent to prevent coking, simultaneously also
Oxidant be may be used as to promote the hydrocarbon pyrolysis.The hydrocarbon pyrolysis system of Fig. 1 is the lab setup provided for this following discussion；So
And, it should be appreciated that system and method covers other configurations, including extensive and industrial process scheme.
With reference to the embodiment of Fig. 1, it is shown that for cracking the hydrocarbon pyrolysis system 100 of the laboratory scale of hydrocarbon charging 4.Specifically
Ground, hydrocarbon pyrolysis system 100 carry out the catalysis hydrocarbon pyrolysis of hydrocarbon charging 4 in the presence of exothermic material (HGM) stream 2.
Hydrocarbon charging 4 can refer to any hydrocarbon source derived from petroleum, coal liquid or biomaterial.The example in hydrocarbon source includes gamut
Crude oil, distill the crude oil, Residual oil, top crude oil, liquefied petroleum gas (LPG), naphtha, gas oil, the product stream from oil plant,
Product stream, liquefaction coal from steam-cracking process, product liquid, pitch, oil shale, the biology recycled from oil or tar sand
Matter hydrocarbon etc..Will in the specific example described in subsequent paragraph, hydrocarbon charging 4 may include n-hexane, naphtha, mixed butene,
Ethylene and combinations thereof.
Mixed butene is conventionally considered as the stream than propylene and ethylene more low value.Pure butene-1 has raw for polyethylene
The value of production, but since by the technical difficulty of itself and mixed butene flow separation, butene-1 typically selectively passes through such as ethylene two
Dimerization is produced at the direct method of butene-1.Demand to propylene has substantially exceeded the demand to ethylene, therefore can cut down pair
The sale of ethylene, and remaining ethylene is fed back into cracking reactor to generate more propylene.It can be based on to product
Demand adjusts the feeding flow of hydrocarbon pyrolysis process, to generate the most desirable final product.
HGM stream 2 may include can be used for cracking process for generating exothermic various components.In one or more embodiments
In, HGM includes at least one aldehydes or ketones.In one or more embodiments, aldehyde is formaldehyde.Since formaldehyde is gaseous state at room temperature
, therefore its 37 mass % distribution usually to be dissolved in water.This mixture is commonly referred to as 100% formalin.As steady
Determine agent, can add methanol in formalin to prevent block and polymerization.It is not limited to theory, the formaldehyde conduct containing methanol
HGM is carried out well, because it was surprisingly found that for example formaldehyde is converted into CO and H2Predictable side reaction increased simultaneously
Hydrocarbon inhibited.
In one or more embodiments, the other HGM in addition to ketone or aldehyde flows 2 components, such as formaldehyde, it may include one
Kind or a variety of other aldehyde, ketone or alcohol in addition.A variety of aldehyde, ketone, alcohol or combinations thereof is mixed to peomote or hinder to certain
The selectivity of reaction product.For example, reaction product can with the variation of other aldehyde, ketone or alcohol and the ratio of formaldehyde or other aldehyde
It shifts to or far from light olefin.
Contemplate the formaldehyde of various concentration in formalin and carbinol mixture.For example, formalin (37 weight % formaldehyde
Aqueous solution) can undiluted or diluted form use, required concentration needed for the air speed to reach specific cleavage reaction.One
In a or multiple embodiments, HGM 2 may include the formaldehyde of 5 to 37 weight % or the formaldehyde or 20 to 37 weights of 10 to 37 weight %
Measure the formaldehyde of % or the formaldehyde of 25 to 37 weight %.The component of HGM stream 2 can be obtained from renewable resource.Specifically, such as
The component of aldehyde, ketone and alcohol can be obtained from the fermentation process of biomass or synthesis gas process.
Referring again to FIGS. 1, hydrocarbon pyrolysis system 100 may include the reactor system at least one catalyst bed reactor 10
System, and optional other reactor and unit.For example, these other option units may include being connected at least one to urge
The preheater reactor 12 and other heater or heat exchanger 18 of agent bed reactor 10.At industrial scale, the hydrocarbon pyrolysis
System 100 also may include the reactor assembly of not catalyst bed reactor.For example, it is contemplated to there is no the case where catalyst
Under, utilize the hydrocarbon pyrolysis system 100 of thermal cracking.
As shown in the laboratory scale experiments room scale reaction device system of Fig. 1, catalyst bed reactor 10 may include setting
Solid acid catalyst bed 14 in catalyst bed reactor 10.As previously mentioned, the operation of catalyst bed reactor 10 leads to hydrocarbon
The cracking of charging 4 is to generate pyrolysis product 40, and wherein pyrolysis product 40 includes light C1-C4Hydrocarbon, such as ethylene and propylene, Yi Jichong
C5+ hydrocarbon.Pyrolysis product 40 may include ethylene, propylene, butylene, benzene,toluene,xylene, ethylo benzene, H2, methane, ethane, LPG,
Naphtha, gasoline and gas oil.The specific combination of product depends on being fed to catalyst bed reactor 10 in pyrolysis product 40
Component.Addition HGM stream 2 reduce or eliminates the other thermal energy in catalyst bed reactor 10 to catalyst bed reactor 10
Input demand.Specifically, HGM stream 2 undergoes exothermic reaction in catalyst bed reactor 10, counteracts endothermic cracking process,
Produce neutral whole hydrocarbon pyrolysis operation.Component, flow velocity or both the component and flow velocity for changing HGM stream 2 can produce heat
The whole hydrocarbon pyrolysis of negativity to neutral to the hot positive operates.
It is intended for the various components of the solid acid catalyst bed 14 of catalyst bed reactor 10.Implement in one or more
In example, solid acid catalyst bed 14 may include aluminosilicate zeolite, silicate (such as silicalite) or titan silicate.Further
Embodiment in, solid acid catalyst be with Substituted Mordenite invert (Mordenite Framework Inverted)
(MFI) aluminosilicate zeolite of structure.Such as but without limitation, the aluminosilicate zeolite catalyst of MFI structure can be
ZSM-5 catalyst.In another embodiment, ZSM-5 catalyst can be H-ZSM-5 catalyst, wherein at least a part of
ZSM-5 catalyst ion exchange position is occupied by H+ ion.In addition, aluminosilicate zeolite catalyst, such as H-ZSM-5 catalysis
Agent can have at least 10 Si/Al molar ratio.In a further embodiment, aluminosilicate zeolite catalyst can have at least
30, or at least 35, or at least 40 Si/Al molar ratio.In addition, aluminosilicate zeolite catalyst may also include for changing sial
The structure of hydrochlorate zeolite catalyst and one or more other components of performance.Specifically, aluminosilicate zeolite catalyst can
Including phosphorus, boron, nickel, iron, tungsten, other metals or combinations thereof.In various embodiments, aluminosilicate zeolite catalyst may include 0-
The other component of the other component of 10 weight %, the other component of 1-8 weight % or 1-5 weight %.Such as but do not make
For limitation, these other components can in ZSM-5 wet impregnation, then drying and calcination.Aluminosilicate zeolite catalyst can
Contain central hole structure.The size of catalyst is set to the diameter with 25 to 2,500 microns (μm).In further embodiment
In, catalyst can have 400 to 1200 μm, 425 to 800 μm, 800 to 1000 μm or 50 to 100 μm of diameter.Catalyst granules
Minimum dimension depend on reactor design, with prevent catalyst granules pass through have reaction product filter.
In one or more embodiments, catalyst bed reactor 10 can be fixed bed reactors, fluidized-bed reactor,
Slurry reactor or moving-burden bed reactor.In a specific embodiment, catalyst bed reactor 10 is fixed bed reactors.?
In some embodiments with fixed bed reactors, combined hydrocarbon charging 4 and heating material stream 2 are in catalyst bed reactor 10
Residence time be in the range of 0.05 second to hour.For example, can for the residence time of diesel oil hydrogenation treatment liquid charging
Close to 1 hour, and FCC application in generally at 0.1 to 5 second in the range of.Therefore, in various embodiments, catalyst
Residence time in bed reactor 10 is 0.1 second to 5 seconds or 5 minutes to 1 hour.The combined hydrocarbon for the best hydrocarbon pyrolysis into
Residence time needed for material 4 and the fixed bed reactors of heating material stream 2 depends on solid acid catalyst bed 14, hydrocarbon charging 4
With the operation temperature and composition of heating material stream 2.In addition, in one or more embodiments, bed voidage is indicated by sky
Volume fraction occupied by gap is between 0.2 and 1.0.In a further embodiment, bed voidage is in 0.3 and 0.8
Between.
Catalyst bed reactor 10 can have 250 to 850 DEG C of operation temperature.In a further embodiment, catalyst
Bed reactor 10 has 450 to 650 DEG C or 540 to 560 DEG C or 575 to 595 DEG C of operation temperature.It is not limited to theory, is recognized
The catalyst life of solid acid catalyst bed 14 can be improved for addition HGM 2.HGM 2 be used as diluent and aoxidize hydrocarbon charging with
Prevent coking.
In addition, solid acid catalyst bed 14 can under enough flow velocitys containing heating nitrogen 6 and oxygen air-flow in quilt
Preheating, to heat solid acid catalyst bed 14.Oxygen can be used as air offer.In various embodiments, the air-flow of preheating is 250
It is heated to 650 DEG C or 475 to 525 DEG C or 490 to 510 DEG C.
With reference to Fig. 1, laboratory scale reactor assembly, the method may additionally include the upstream of catalyst bed reactor 10
Preheat hydrocarbon charging 4.This preheating of hydrocarbon charging 4 can be realized in preheater reactor 12.As shown, hydrocarbon charging 4 can be
It is heated in the presence of nitrogen 6.In one embodiment, preheater reactor 12 can will be supplied to the hydrocarbon of catalyst bed reactor 10
The temperature of charging 4 is improved at least 100 DEG C of pre-reaction temperature.Hydrocarbon charging 4 is usually heated to 200-300 DEG C of pre-reaction temperature
Degree.This pre-reaction temperature range remains sufficiently low to prevent the heat in the preheater reactor 12 before catalyst bed reactor 10
Cracking.On the contrary, pre-reaction temperature is sufficiently high, so that cold hydrocarbon charging 4 will not make catalyst bed 14 close to catalyst bed reactor 10
Entrance it is cooling and influence the total conversion of hydrocarbon charging 4.In one or more embodiments, hydrocarbon pyrolysis system 100 can also be optional
Ground includes at least one hydrocarbon preheater 18 that the upstream of preheater reactor 12 is arranged in.Hydrocarbon preheater or preheater
(preheater/preheaters) 18, as shown in Figure 1, improving the hydrocarbon charging for being supplied at least one preheater reactor 12
Temperature.Preheater 18 may include heat exchanger known to those of ordinary skill in the art or similar heater assembly.
Hydrocarbon pyrolysis system 100 may also include be arranged in the upstream of catalyst bed reactor 10 at least one exothermic material it is pre-
Hot device 16.Exothermic material preheater 16 improves the temperature for being supplied to the heating material stream 2 of at least one catalyst bed reactor 10.
In embodiment, the temperature of heating material stream 2 is increased at least 100 DEG C of pre-reaction temperature by exothermic material preheater 16.Hair
The maximum pre-reaction temperature of hot material stream 2 is limited by the cracking temperature of heating material stream 2, thus the heat of heating material stream 2
Cracking does not occur before catalyst bed reactor 10.In the reactor of laboratory or pilot-scale, hydrocarbon pyrolysis system 100 is also
It may include other heating elements as shown in the figure.For example, hydrocarbon pyrolysis system 100 may include reactor furnace 20 or around catalyst
The hot tank 22 of bed reactor 10, preheater reactor 12, exothermic material preheater 16 and hydrocarbon preheater 18.Reactor furnace 20 can have
Help keep the temperature of catalyst bed reactor 10 and preheater reactor 12.Similarly, hot tank 22 is for keeping catalyst bed
Heat around reactor 10, preheater reactor 12, exothermic material preheater 16 and hydrocarbon preheater 18, to reduce heat loss.
Hydrocarbon preheater 19, preheater reactor 12 and exothermic material preheater 16 can also be combined into single preheater, with
The temperature of hydrocarbon charging 4 and heating material stream 2 is improved before entering catalyst bed reactor 10.
In commercial scale operation, hydrocarbon charging 4 and heating material stream 2 are heated until hydrocarbon charging 4 and heating material stream 2
Until vaporizing respectively.Hydrocarbon charging 4 and heating material stream 2 may be mixed together and in single feed preheater while vaporizing.
Alternatively, hydrocarbon charging 4 and heating material stream 2 can be only with isolated feed preheater before group is merged into and expects cracking reactor
On the spot vaporize.Then, the hydrocarbon of vaporization can be injected by the steam of heating or other diluents before being fed to cracking reactor
In the combination vaporization stream of charging 4, the heating material stream 2 of vaporization or hydrocarbon charging 4 and heating material stream 2.To cracking reactor into
Diluent is provided in material, intermolecular by hydrocarbon charging 4 separates.It should be understood that when using formalin, (37 weight % formaldehyde are water-soluble
Liquid) group timesharing as heating material stream 2, it may not be necessary to steam or other diluents are added, because formalin is included in
The water of steam is converted into the vaporescence of heating material stream 2.It is further appreciated that the vaporization of hydrocarbon charging 4 and heating material stream 2 can
To realize inside cracking reactor rather than before injecting in reactor.
In addition, the amount of balance heating material stream 2 and hydrocarbon charging 4 can promote neutral cracking process.Further real
It applies in example, HGM stream 2 and hydrocarbon charging 4 with the weight ratio of 1:10 to 10:1 are fed to catalyst bed reactor 10.Further real
It applies in example, heating material stream 2 and hydrocarbon charging 4 is fed to catalyst bed with the ratio of 1:6 to 6:1,1:3 to 3:1 or 1:2 to 2:1
Reactor 10.In a still further embodiment, heating material stream 2 and hydrocarbon charging 4 are fed to catalysis with the ratio of 2:3 to 3:2
Agent bed reactor 10.
Referring again to FIGS. 1, pyrolysis product 40 may include various light C1-C4Hydrocarbon and weight C5+Hydrocarbon.In one or more embodiments
In, pyrolysis product 40 specifically includes propylene, butylene such as 2- trans-2-butene, n-butene, isobutene and 2- cis-butene, C5Alkene,
Aromatic hydrocarbons, methane, ethane, propane, butane and pentane.The component of pyrolysis product 40 depends on the group of hydrocarbon charging 4 and heating material stream 2
Point.It for example, formaldehyde provides heat not only to offset endothermic cracking process, but also is the effecting reaction object for producing light olefin.
In order to separate the lighter hydrocarbons in pyrolysis product 40 with heavy hydrocarbon, hydrocarbon pyrolysis system 100 may also include condenser and at least
One liquid/gas separator 24.Liquid/gas separator 24 may include flash of light slot etc..Pyrolysis product 40 is leaving cracking reactor
When be fed in condenser, wherein gaseous breakdown products 40 temperature reduce and partial condensation.Then partial condensation charging is sent
Liquid/gas separator 24 is expected, wherein separating liquid and gas.Specifically, it in liquid/gas separator 24, can separate as gas
The light hydrocarbon stream 42 of phase lighter hydrocarbons, and liquid phase heavy hydrocarbon stream 44 is then discharged from liquid/gas separator 24 respectively.In addition, at industrial scale,
In order to separate hydrocarbon from the heavy hydrocarbon in pyrolysis product 40, hydrocarbon pyrolysis system 100 may include voluminous object destilling tower.Using destilling tower,
The commercial scale of stripper or extraction tower separates and is this field with other method and process of separation product stream for handling
Technical staff is known and can comparably use.
It is expected that further reaction is to separate required propylene and ethylene with light hydrocarbon stream 42.For example, light hydrocarbon stream 42 can be with
As liquid hydrocarbon product cooling and collect.When boundary, propylene and ethylene can be separated by distillation, extractive distillation or membrane separating method.
In a further embodiment, adjust HGM stream 2, hydrocarbon charging 4 and be supplied to hydrocarbon pyrolysis system 100 steam or its
The overall flow rate of its diluent is to control the air speed of reaction.Weight (hourly) space velocity (WHSV) (WHSV) be defined as reactant flow (for example, with gram/
Hour (g/hr) is unit) divided by the weight (such as with gram (g) for unit) of catalyst weight.The flow of reactant includes HGM
The total flow of stream 2, hydrocarbon charging 4 and steam or other diluents.In one or more embodiments, the weight (hourly) space velocity (WHSV) of reaction is
0.01 to 100 hour-1(h-1).In a further embodiment, the weight (hourly) space velocity (WHSV) of reaction is 1 to 8 hour-1, 2 to 4 hours-1Or
2.8 to 3.4h-1。
Ethylene and propylene are two kinds of main petrochemical industry basic materials for various applications, such as the life of plastics and synthetic fibers
It produces.Specifically, ethylene is widely used in manufacture polyethylene, ethlyene dichloride and ethylene oxide, to packaging, plastic processing, building and
Textile industry is highly useful.In addition, propylene is commonly used to manufacture polypropylene, but it is also production propylene oxide, acrylic acid and is permitted
Base product necessary to mostly other chemical derivatives.Plastic processing, packaging industry, furniture industry and auto industry be propylene and
The common user of its derivative.Therefore, it is necessary to increase the yield of light olefin such as ethylene and propylene to supply numerous industrial users.
The improved conversion ratio of hydrocarbon charging 4 and light olefin (for example, ethylene and propylene) is verified with experiment test.?
Different condition and with different 2 ratios of heating material stream in the case where, hexane be provided to hydrocarbon pyrolysis system 100 experiment dress
It sets.
Example
Following instance is the explanation to the embodiment of the present invention, and is not intended to be limited to the range of embodiment described in the disclosure.
Experimental data is obtained to show that the influence in conjunction with HGM is reacted in the hydrocarbon pyrolysis.Catalysis reaction operates under atmospheric pressure
It is carried out in flow reactor of fixed bed.To be fitted into reactor with 9 to the catalyst of 12g mass, the catalyst padded with
Pallet is simultaneously sized to 425-800 microns of diameter (μm).Catalyst is available from Nankai University catalyst Co. (Nankai
University Catalyst Co.) ZSM-5 micro porous molecular sieve.Before catalysis reaction, catalyst is containing N2
(120cm3 min-1) air-flow in activation to required reaction temperature and keep whole night.Using 3 area's electric heaters by fixed bed stream
Dynamic reactor is heated to required reaction temperature.Under required reaction temperature (usually between 250-850 DEG C), reactant,
It is selected from n-hexane, naphtha and formaldehyde (the 37% stable solution in 13.88% methanol), is introduced into reactor to start
Reaction.
Pass through the on-line gas chromatography point equipped with Agilent HP-Al/KCl (50m × 0.53mm ID, 15 μm) column
Analysis carrys out the product of self-catalyzed reaction, and is detected by flame ionization detector (FID) detector.N2、CH4、C2H6、C2H4、
C3H8、C3H6, positive C4H10, different C4H10、1-C4H8, the cis- C of 2-4H8, trans--the C of 2-4H8, different C4H8, positive C5H12With positive C5H6It is used as
Calibration standard.By flow reactor of fixed bed outlet gas chromatograph between all pipelines and valve be heated to 105 DEG C with
Prevent the condensation of heavier hydrocarbon.
Product liquid is collected respectively using low pressure liquid/gas separator.Organic moiety (if any) is separated from water, and
Its composition is analyzed to identify product by gaschromatographic mass spectrometry (GCMS), and then by gas-chromatography (GC), to measure its dense
Degree.
The conversion ratio determination of hexane is weight percentage.Conversion ratio is defined as being converted into the hundred of the hexane weight of final product
Divide ratio.The equation such as equation (1) of hexane conversion provides, wherein WiIt is the weight for injecting hexane, WfBe the unreacted that detects of GC oneself
The weight of alkane.
Conversion ratio %=100 × (Wi-Wf)/Wi (1)
In addition, as previously defined, reciprocal of duty cycle (WHSV) is at the constant of test subset for comparing HGM effect when heavy
It is kept.
During the experiment, the normal reaction time is 35 minutes.After reaction, catalyst bed high-purity nitrogen with
The flow velocity of 0.2liters/min purges 30 minutes, to wash away all reaction products and hydrocarbon before introducing air.The introducing of air
It is delayed by, because it can be burning Harm and control in the presence of hydrocarbon and reaction product.With nitrogen rinse with remove reaction product and
After hydrocarbon, using 0.154lit/min air velocity regenerated catalyst 1 hour or until temperature is stablized.Later, by catalyst
Bed rinses 30 minutes with nitrogen again to remove combustion product
Hexane is used to be tested as hydrocarbon charging 4 and formaldehyde as heating material stream 2, to show the effect of exothermic material
Fruit.Each test run 35 minutes.Table 1 is described in detail when formaldehyde exists and in the absence of formaldehyde, is used for pyrolysis product 40
Various cracking process parameters.The combination of hexane and formaldehyde leads to C6Conversion ratio, ethylene yield and productivity of propylene increase.
Table 1
When heating material stream 2 provides together with hydrocarbon charging 4, the yield increase of ethylene and propylene is needed.In addition, table
2, it is following provided, the various cracking when formaldehyde exists and residence time variation, for pyrolysis product 40 are described in detail
Procedure parameter.Each test run 35 minutes.Residence time increase leads to C6Conversion ratio increases.
Table 2
When adding heating material stream 2, the neutral of hydrocarbon pyrolysis process may refer to Fig. 2 and 3.Specifically, Fig. 2 shows to work as
When hexane and exothermic material are provided with the ratio of 2:1, the temperature of caused solid acid catalyst bed 14, which declines, to be reduced.When introducing oneself
When alkane is fed, the temperature bed of solid acid catalyst bed 14 declines very big, and then controller passes through increase catalyst bed
The wall temperature of reactor 10 responds.Exothermic material is not generated using only hexane feed (hydrocarbon charging 4) and, the increase of wall temperature will not picture
Temperature in catalyst bed reactor 10 from the endothermic reaction declines so fast.On the contrary, simultaneously by heating material stream 2 and oneself
Alkane stream (hydrocarbon charging 4) is concomitantly introduced into catalyst bed reactor 10, the temperature of solid acid catalyst bed 14 by less interference,
Because the less external input heating from controller is due to exothermic material and its catalyst bed reactor of exothermic reaction 10
Wall is required.
Similarly, with reference to Fig. 3, it can be seen that when adding heating material stream 2, hydrocarbon pyrolysis process is neutral.Specifically,
Fig. 3 shows that, when hexane and exothermic material are provided with the ratio of 1:2, the temperature decline of caused solid acid catalyst bed 14 is disappeared
It removes.Relative to hexane (hydrocarbon), the exothermic material of larger percentage causes the temperature of solid acid catalyst bed 14 to improve immediately.Phase
Instead, in the case where no heating material stream 2, the temperature of solid acid catalyst bed 14 over time slowly start to increase
Decline immediately before.
It should be noted that the solid acid catalyst in solid acid catalyst bed does not have after operation 35 minutes in illustrative example
It shows to decay.
It will now be appreciated that describe cracking hydrocarbon charging method various aspects, and these aspect can with it is various its
He is used in combination aspect.
In a first aspect, the disclosure provides a kind of method for cracking hydrocarbon charging.The method includes to split hydrocarbon charging introducing
Solve reactor in, by comprising at least one aldehydes or ketones exothermic material (HGM) stream is introduced into cracking reactor, vaporization hydrocarbon charging with
HGM stream, and cracking hydrocarbon charging is to generate pyrolysis product.Pyrolysis product includes C1-C4Hydrocarbon and C5+ hydrocarbon.
In second aspect, the disclosure provides the method for first aspect, and wherein hydrocarbon charging and HGM stream are introducing cracking reactor
In after vaporize.
In the third aspect, the disclosure provides the method for first aspect, and wherein hydrocarbon charging and HGM stream are introducing cracking reactor
In before vaporize.
In fourth aspect, the disclosure provides the first method for arriving either third aspect face, and wherein HGM stream includes ketone.
At the 5th aspect, the disclosure provides the first method for arriving either fourth aspect face, and wherein HGM stream includes aldehyde.
At the 6th aspect, the disclosure provides the method for the 5th aspect, and wherein aldehyde is dissolved in the formaldehyde in water.
The 7th aspect, the disclosure provide the 6th aspect method, wherein the formaldehyde being dissolved in water with organic solvent come
Stablize.
In eighth aspect, the disclosure provides the method for the 7th aspect, and wherein organic solvent is methanol.
At the 9th aspect, the disclosure provides the first method for arriving either eighth aspect face, wherein the further packet of HGM stream
Alcohol-containing, ketone in addition or other aldehyde.
At the tenth aspect, the disclosure provides the method in either the first to the 9th aspect face, and wherein pyrolysis product includes
Ethylene, propylene, butylene, benzene,toluene,xylene, ethylo benzene, H2, methane, ethane, LPG, naphtha, gasoline and gas oil.
On the one hand the tenth, the disclosure provides the method in either the first to the tenth aspect face, wherein cracking reactor
It is at least one catalyst bed reactor.
At the 12nd aspect, the disclosure provides the method for the tenth one side, and wherein catalyst bed reactor includes that setting exists
Solid acid catalyst bed in catalyst bed reactor, and catalyst bed reactor is the reaction temperature at 250 to 850 DEG C.
At the 13rd aspect, the disclosure provides the method for the 11st or the 12nd aspect, wherein catalyst bed reactor packet
Containing fluidized-bed reactor, fixed bed reactors, slurry reactor or moving-burden bed reactor.
In fourteenth aspect, the disclosure provides the method for the 11st or the 12nd aspect, and wherein catalyst bed reactor is
Fixed bed reactors.
At the 15th aspect, the disclosure provides the 12nd method for arriving either fourteenth aspect face, wherein solid acid
Catalyst is ZSM-5 catalyst.
At the 16th aspect, the disclosure provides the method for the 15th aspect, and wherein ZSM-5 catalyst is at least 10
Si/Al molar ratio.
At the 17th aspect, the disclosure provides the method for the 15th aspect, and wherein ZSM-5 catalyst is at least 30
Si/Al molar ratio.
The 18th aspect, the disclosure provide the 15th aspect method, wherein ZSM-5 catalyst include phosphorus, boron, nickel,
Iron, tungsten or combinations thereof.
At the 19th aspect, the disclosure provides the method in either the first to the 18th aspect face, wherein HGM stream and hydrocarbon
Feeding flow is fed with the weight ratio of 1:10 to 10:1.
At the 20th aspect, the disclosure provides the method in either the first to the 19th aspect face, wherein hydrocarbon charging stream
Comprising not being fractionated or being fractionated crude oil, hexane, naphtha, mixed butene, ethylene and combinations thereof.
It will be apparent to one skilled in the art that the case where not departing from the spirit and scope of required theme
Under, described embodiment can be carry out various modifications and be changed.Therefore, it is intended that this specification covering is described herein
The modifications and variations of various embodiments, condition are that such modifications and variations fall in the model of appended claims and its equivalent
In enclosing.
Through the disclosure, range is provided.It is contemplated that in each discrete value that range is covered is also included within.In addition, can
It is also envisioned that the range formed by each discrete value that clear scope of disclosure is covered.
Claims (20)
1. a kind of method for cracking hydrocarbon charging, it includes:
Hydrocarbon charging is introduced into cracking reactor；
Exothermic material (HGM) stream comprising at least one aldehydes or ketones is introduced into the cracking reactor；
Vaporize the hydrocarbon charging and HGM stream；With
The hydrocarbon charging is cracked to generate pyrolysis product, wherein the pyrolysis product includes C1-C4Hydrocarbon and C5+ hydrocarbon.
2. according to the method described in claim 1, wherein the hydrocarbon charging and HGM stream are after being introduced into the cracking reactor
Vaporization.
3. according to the method described in claim 1, wherein the hydrocarbon charging and HGM stream are before being introduced into the cracking reactor
Vaporization.
4. according to the method described in claim 1, wherein the HGM stream includes ketone.
5. according to the method described in claim 1, wherein the HGM stream includes aldehyde.
6. according to the method described in claim 5, wherein the aldehyde is dissolved in the formaldehyde in water.
7. according to the method described in claim 6, wherein the formaldehyde being dissolved in water is stablized with organic solvent.
8. according to the method described in claim 7, wherein the organic solvent is methanol.
9. according to the method described in claim 1, wherein the HGM stream further includes alcohol, ketone in addition or other aldehyde.
10. according to the method described in claim 1, wherein the pyrolysis product includes ethylene, propylene, butylene, benzene, toluene, two
Toluene, ethylo benzene, H2, methane, ethane, LPG, naphtha, gasoline and gas oil.
11. according to the method described in claim 1, wherein the cracking reactor is at least one catalyst bed reactor.
12. according to the method for claim 11, wherein the catalyst bed reactor includes being arranged in the catalyst bed
Solid acid catalyst bed in reactor, and the catalyst bed reactor is the reaction temperature at 250 DEG C to 850 DEG C.
13. according to the method for claim 12, wherein the catalyst bed reactor includes fluidized-bed reactor, fixed bed
Reactor, slurry reactor or moving-burden bed reactor.
14. according to the method for claim 13, wherein the catalyst bed reactor is fixed bed reactors.
15. according to the method for claim 12, wherein the solid acid catalyst is ZSM-5 catalyst.
16. according to the method for claim 15, wherein the ZSM-5 catalyst has at least 10 Si/Al molar ratio.
17. according to the method for claim 15, wherein the ZSM-5 catalyst has at least 30 Si/Al molar ratio.
18. according to the method for claim 15, wherein the ZSM-5 catalyst includes phosphorus, boron, nickel, iron, tungsten or its group
It closes.
19. according to the method described in claim 1, wherein the HGM stream and the hydrocarbon charging stream are with the weight of 1:10 to 10:1
Than charging.
20. according to the method described in claim 1, wherein the hydrocarbon charging stream includes not to be fractionated or be fractionated crude oil, hexane, stone brain
Oil, mixed butene, ethylene and combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662335187P | 2016-05-12 | 2016-05-12 | |
| US62/335,187 | 2016-05-12 | ||
| PCT/US2017/030720 WO2017196594A1 (en) | 2016-05-12 | 2017-05-03 | Internal heat generating material coupled hydrocarbon cracking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109153921A true CN109153921A (en) | 2019-01-04 |
Family
ID=58699307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780028865.0A Pending CN109153921A (en) | 2016-05-12 | 2017-05-03 | The inner heat material combination hydrocarbon pyrolysis |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20170327750A1 (en) |
| EP (1) | EP3455332A1 (en) |
| JP (1) | JP6895993B2 (en) |
| KR (1) | KR20190007453A (en) |
| CN (1) | CN109153921A (en) |
| SA (1) | SA518400402B1 (en) |
| SG (2) | SG10202011092RA (en) |
| WO (1) | WO2017196594A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220064548A1 (en) * | 2020-09-01 | 2022-03-03 | Saudi Arabian Oil Company | Integrated process for conversion of whole crude to light olefins |
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- 2017-05-02 US US15/584,598 patent/US20170327750A1/en not_active Abandoned
- 2017-05-03 EP EP17722976.2A patent/EP3455332A1/en active Pending
- 2017-05-03 JP JP2018559354A patent/JP6895993B2/en active Active
- 2017-05-03 CN CN201780028865.0A patent/CN109153921A/en active Pending
- 2017-05-03 WO PCT/US2017/030720 patent/WO2017196594A1/en unknown
- 2017-05-03 KR KR1020187035752A patent/KR20190007453A/en not_active Application Discontinuation
- 2017-05-03 SG SG10202011092RA patent/SG10202011092RA/en unknown
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| GB315991A (en) * | 1928-07-07 | 1929-07-25 | Ig Farbenindustrie Ag | Improvements in the conversion of hydrocarbons of high boiling point into others of low boiling point |
| CN86101079A (en) * | 1984-06-21 | 1987-12-23 | 无比石油公司 | The cracking of disperse type catalyzer when methyl alcohol exists |
| US5026936A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of propylene from higher hydrocarbons |
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| US20130060070A1 (en) * | 2011-09-01 | 2013-03-07 | University Of Massachusetts | Method for producing fluid hydrocarbons |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3455332A1 (en) | 2019-03-20 |
| JP2019518824A (en) | 2019-07-04 |
| KR20190007453A (en) | 2019-01-22 |
| JP6895993B2 (en) | 2021-06-30 |
| SA518400402B1 (en) | 2022-02-28 |
| US20170327750A1 (en) | 2017-11-16 |
| SG10202011092RA (en) | 2020-12-30 |
| SG11201809876RA (en) | 2018-12-28 |
| WO2017196594A1 (en) | 2017-11-16 |
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