CN105085143A - Method for producing ethylene and propylene by mixing C five-carbon hexaalkane and C four - Google Patents
Method for producing ethylene and propylene by mixing C five-carbon hexaalkane and C four Download PDFInfo
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- CN105085143A CN105085143A CN201510219120.5A CN201510219120A CN105085143A CN 105085143 A CN105085143 A CN 105085143A CN 201510219120 A CN201510219120 A CN 201510219120A CN 105085143 A CN105085143 A CN 105085143A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 123
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 title abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000005977 Ethylene Substances 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000002994 raw material Substances 0.000 claims abstract description 83
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 78
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 62
- 239000000047 product Substances 0.000 claims description 37
- -1 ethylene, propylene Chemical group 0.000 claims description 31
- 239000002808 molecular sieve Substances 0.000 claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 30
- 239000004480 active ingredient Substances 0.000 claims description 21
- 238000005336 cracking Methods 0.000 claims description 18
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000003502 gasoline Substances 0.000 claims description 5
- 241000269350 Anura Species 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 description 26
- 150000002430 hydrocarbons Chemical class 0.000 description 25
- 239000004215 Carbon black (E152) Substances 0.000 description 18
- 238000007233 catalytic pyrolysis Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000004567 concrete Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical class [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical class C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for producing ethylene propylene by mixing C-V-hexaalkane and C-IV, wherein a raw material rich in C-V-hexaalkane is firstly put into a reactor filled with a dehydrogenation catalyst at the temperature of 480-700 ℃, the pressure of 0.01-3 MPa and the volume space velocity of 0.1-10 h-1After alkane dehydrogenation reaction is carried out under the condition, a dehydrogenation product and carbon tetrahydrocarbon are mixed according to the mass ratio of 0.1: 1-10: 1, and then the mixture enters a reactor filled with a catalytic cracking catalyst, the temperature is 450-650 ℃, the pressure is 0.1-3 MPa, and the volume space velocity is 0.1-10 h-1The catalytic cracking reaction is carried out under the condition. The application of the invention has the advantages of lower reaction temperature of olefin catalytic cracking than alkane catalytic cracking, reduced energy consumption and high yield of ethylene and propylene.
Description
Technical field
The invention provides a kind of raw material refinery being rich in carbon five carbon six alkanes, through mixing with C_4 hydrocarbon after dehydrogenation catalyst contact catalysis dehydrogenation in dehydrogenation reactor, contact with catalytic cracking catalyst in catalytic cracking reaction device, carry out catalytic cracking reaction, produce the method for ethylene, propylene.
Background technology
In recent decades, along with the development of global economy, market is to the demand of ethylene, propylene also in continuous increase, and the raw material of alkene industry and technique are to diversification, new technology future development.In the presence of a catalyst, deep catalytic cracking technology petroleum hydrocarbon being carried out to high-temperature catalytic cracking increasing output of ethylene propylene has become the important technical solving low-carbon alkene shortage at present, and more biases toward lightweight material in the selection of fcc raw material.
Enter 12, along with the propelling of the projects such as CNPC's Guangdong petrochemical industry 2,000 ten thousand tons/year oil refining, the oil refining of 1,000 ten thousand tons/year, Kunming, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, Fushun petrochemical industry 800,000 tons/year of ethene, Daqing petrochemical 1,200,000 tons/year of expansion of ethylene, oil-refining capacity and the ethene production capacity of CNPC also will expand further, and the output of the C5/C6 alkane (as reforming topped oil, hydrogenation coking light naphthar, pentane wet goods) of refinery's by-product, catalytic cracking C4 and c4 cleavage resource is also significantly increasing.C5/C6 alkane is not high because of itself octane value, can not, directly as motor spirit, need to process upgrading further.C4 resource is except part is for the production of except MTBE, alkylate oil, polymerization single polymerization monomer, and major part is burnt as domestic fuel.And C4 hydrocarbon and tops are not only cheap, and transportation cost is high, in transportation loss large, concerning this refinery, belong to low-value product.
CN101348409A discloses a kind of method of being produced low-carbon alkene by petroleum hydrocarbon.Petroleum hydrocarbon raw material is carried out dehydrogenation reaction by dehydrogenation reactor by the method, obtains the petroleum hydrocarbon logistics containing unsaturated hydrocarbons compounds; Again this logistics is mirrored olefin reactor reaction, finally introduce separation circuit and carry out separation and obtain C2 ~ C4 logistics.The method adds separation system in order to reduce olefin hydrocarbon reactor treatment capacity after dehydrogenation reactor, using following for part C4 gaseous stream as heat source, does like this and certainly will consume part material, is wasted by part ethylene, propylene target product simultaneously.The method is all introduced separation system and is considerably increased cost input like this before and after conversion of olefines, and flow process is complicated, and energy consumption is also higher.
CN201110100093.1 discloses a kind of method adopting light hydrocarbon feedstocks dehydrogenation and cracking to prepare ethene, propylene.First the method carries out Dehydroepiandrosterone derivative to light hydrocarbon feedstocks, generate alkene and enter into catalytic cracking reaction device further, obtain split product ethylene, propylene, more than the C4 hydro carbons separated in split product returns cat-cracker to carry out circulating reaction and obtains object product, but for the situation that recycle stock Determination of Alkane Content is higher, dehydrogenation further, does not directly carry out catalytic pyrolysis, such energy consumption is higher, restriction ethylene, propylene yield.
CN201010204374.7 discloses a kind of method of increasing output of ethylene propylene.Method of the present invention be with from the butane of refinery and alkene for raw material, first enter into catalytic cracking system reaction, then enter dehydrogenation reaction alkene butane dehydrogenation is obtained ethylene, propylene.The present invention adopt the first cracking of technique after the dehydrogenation main raw material that is applicable to be butane, carbon more than four alkane is not suitable for.
The method that CN200710179764.1 proposes petroleum naphtha or solar oil carry out catalytic dehydrogenation catalytic pyrolysis again prepares low-carbon alkene, wherein relate to the reactor that two-step reaction adopts and be fixed-bed reactor, for reducing fixed bed catalyst for cracking coking and deactivation speed, olefin(e) centent in dehydrogenation product must be limited, which greatly limits ethylene, propylene total recovery.
CN200810225944.3 discloses a kind of method being prepared ethylene, propylene by C_4 hydrocarbon.Utilize containing the C4 hydrocarbon of alkane, prepare the method for ethylene, propylene through catalytic dehydrogenation and catalytic pyrolysis process, the raw material that this invention relates to is only limitted to C4 hydro carbons, inapplicable for C5 and above naphtha fraction containing alkane, naphthenic hydrocarbon.
US8080698B2 discloses a kind of plurality of raw materials that adopts through the combination process of cracking Oxidative Dehydrogenation for alkene, by to full distillation gasoline, diesel oil, alkane carries out cracking cracking, and dehydrogenation step prepares butylene, ethene, propylene alkene mixture, this complex process, object product is mainly based on butylene, and ethylene, propylene yield is not high.
US20120071701A1 discloses the method preparing low-carbon alkene with refinery's macromolecule hydrocarbon raw material, fluid catalytic cracking process and FFC are combined with dehydrogenating technology by the method, carry out dehydrogenation after generate longer-chain hydrocarbons being cracked into short-chain hydrocarbons and obtain low-carbon alkene, it is raw material that this technological process is applicable to macromolecule hydrocarbon, also inadaptable for the raw material based on low-carbon alkanes, DeGrain.
Summary of the invention
The object of the present invention is to provide a kind of can by low value-added for refinery be rich in carbon five carbon six alkane and carbon four mixing dehydrogenation after carry out the method for the ethylene, propylene of catalytic pyrolysis production high added value.Contriver thinks by analysis: carried out catalytic dehydrogenating reaction be converted into alkene by be rich in carbon five carbon six alkane and the mixed carbon four of the low value added to refinery's by-product, react under the effect of catalytic cracking catalyst again, alkene is transformed by oligomeric, cracking and disproportionation reaction, and suppress the generation of polycyclic aromatic hydrocarbons and coke, conversion of olefines is made to be the mixture of the ethylene, propylene being rich in high additive value, thus carry feed stock conversion, increase ethylene, propylene productive rate.
Concrete steps of the present invention are: refinery enters catalytic dehydrogenating reaction device and contacts with catalytic dehydrogenation catalyst and carry out catalytic dehydrogenating reaction after being rich in the raw material preheating of carbon five carbon six alkane, catalytic dehydrogenation product and carbon four raw material are mixed into catalytic cracking reaction device and contact with catalytic cracking catalyst and carry out catalytic cracking reaction, catalytic cracking reaction products enters separation system and is separated into dry gas, ethene, propylene, liquefied gas, carbon four C 5 alkane, pyrolysis gasoline component and cracking masout component.
The raw material being rich in carbon five carbon six alkane in the present invention refers to the hydro carbons being main ingredient with carbon five carbon six alkane of refinery's institute's by-product in process of production, as carbon five carbon six hydro carbons etc. that tops, coking light naphthar, pentane oil and other device reclaim, the content of general carbon five and carbon six alkane is more than 45%.
In the present invention, the C_4 hydrocarbon of indication refers to carbon four, catalytically cracked C four, cracking c_4 etc. after the ether of olefin(e) centent more than 35%.
In the present invention, the mass ratio of carbon four raw material and carbon five carbon six paraffinic feedstock is 0.1:1 ~ 10:1.
Be not particularly limited dehydrogenation catalyst in the present invention, be rich in after carbon five carbon six paraffinic feedstock enters catalytic dehydrogenating reaction device after preheating, in catalytic dehydrogenation product, olefin(e) centent is preferably not less than 35%.Dehydrogenation catalyst is preferably made up of carrier and active ingredient, and catalyzer is preferably carrier with high-temperature inorganic oxide, as being TiO
2, Al
2o
3, SiO
2, one or several mixing among ZnO, also can be molecular sieve or molecular sieve and the mixing of above several high-temperature inorganic oxide.Preferably containing at least one metal in VIB, VIII, IA, IIA race is active ingredient, as being Na, Zn, Rb, Cs, Mg, Sr, Ba, Pt, Mo, Cl, F, Br etc., preferably Pt, Cl, Mo, Cr; The content of active ingredient is 0.1% ~ 20% of catalyst weight.It can also be the composite multi-metal oxide catalyst that above-mentioned active ingredient obtains with co-precipitation; Molecular sieve can be one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, aluminium silicophosphate molecular sieve equimolecular sieve, and two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.The shape of catalyzer can be bead, also can be bar shaped.Not specified " % " of the present invention is all weight percentage.
In the present invention, the reaction conditions of catalytic dehydrogenating reaction is preferably: 450 ~ 700 DEG C, pressure 0.01 ~ 3MPa, and liquid volume air speed is 0.1 ~ 10h
-1.The not specified air speed of the present invention is liquid volume air speed.
Be not particularly limited catalytic cracking catalyst in the present invention, catalyzer is preferably containing molecular sieve and one or more active ingredients.Molecular sieve can be specifically ZSM-5, ZSM-8, ZSM-11, ZSM-38, Y type, ZRP, mordenite, SAPO (aluminium silicophosphate) molecular sieve etc., preferred ZSM-5, ZSM-11, ZRP Series Molecules sieve of above molecular sieve, can be one or more in molecular sieve, two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.Catalytic cracking catalyst can contain high-temperature inorganic oxide and molecular sieve, one or more active ingredients, and wherein the resistance to inorganic oxide of high temperature can be ZrO
2, Al
2o
3, SiO
2, among one or several mixing.The active ingredient supported can be selected from the metal of metal as Y, Cr, La, Ce, Mo, W, Mn, Pt, Pd, Zn and Ga of periodictable IIB, III, VB, VIB, VIIB and VIII containing at least one, preferably Y, La, Ce; The active ingredient weight supported is 0.01 ~ 8%.Catalyst shape can be bead, also can be strip.
In the present invention, the reaction conditions of catalytic cracking reaction is preferably: 450 ~ 650 DEG C, pressure 0.1 ~ 3.0MPa, and volume space velocity is 0.1 ~ 10h
-1.
The catalytic dehydrogenating reaction device related in the present invention, catalytic cracking reaction device are fixed-bed reactor, can be that a reactor is used alone, realized by reaction-catalyst regeneration two process intervals, also two or more reactor parallel connection use can carry out cyclical operation, the parallel connection of multiple reactor and series combination can also be divided to use.When the catalyzer in one or several reactor is due to carbon distribution serious inactivation, by switching material import and export, decaying catalyst regeneration Posterior circle uses, the continuous operation of realization response, regeneration system rapidly.
According to an aspect of the present invention, provide a kind of method of producing ethylene, propylene, it comprises the following steps: by be rich in carbon five carbon six alkane raw material preheating after, enter catalytic dehydrogenating reaction device and carry out catalytic dehydrogenating reaction, obtain catalytic dehydrogenation product; After catalytic dehydrogenation product is mixed with carbon four raw material, enter catalytic cracking reaction device and carry out catalytic cracking reaction and obtain catalytic cracking reaction products; And make catalytic cracking reaction products enter separation system, be separated into dry gas, ethene, propylene, liquefied gas, carbon four C 5 alkane, pyrolysis gasoline component and cracking masout component.
In aforesaid method, the raw material being rich in carbon five carbon six alkane is converted into alkene through catalytic dehydrogenation, and carbon four mix after more further catalytic pyrolysis be converted into low-carbon alkene, lighter hydrocarbons low value-added for refinery can be changed into the ethylene, propylene of high additive value.Refinery C five carbon six alkane is through dehydrogenation, after the cracking of C_4 hydrocarbon mixed catalytic, generate ethylene, propylene, yield of ethene can reach 10% ~ 20%, propene yield reaches 20% ~ 50%, diene yield reaches 40% ~ 60%, olefin conversion reaches 80% ~ 90%, the present invention adopts and generates a large amount of alkene by after first for the raw material being rich in carbon five carbon six alkane dehydrogenation, the producing ethene, propylene through catalytic cracking through alkene is mixed again with C_4 hydrocarbon raw material, owing to containing at least one double bond in alkene composition, the alkane that its chemical property comparatively only has singly-bound to form wants active a lot, in catalytic pyrolysis process, required temperature of reaction is low, and ethylene, propylene yield is high.Therefore dehydrogenating technology process energy consumption is less again to adopt the more first cracking of technological process of catalytic pyrolysis after first dehydrogenation.
Further, after the raw material being rich in carbon five carbon six alkane is carried out preheating, the raw material being rich in carbon five carbon six alkane after preheating is contacted with catalytic dehydrogenation catalyst in catalytic dehydrogenating reaction device and carries out catalytic dehydrogenating reaction, obtain catalytic dehydrogenation product; After catalytic dehydrogenation product is mixed with carbon four raw material, make compound enter catalytic cracking reaction device and contact with catalytic cracking catalyst and carry out catalytic cracking reaction, obtain catalytic cracking reaction products.
Further, carbon four raw material and the mass ratio that is rich in carbon five carbon six paraffinic feedstock are 0.1:1 ~ 10:1; Preferably, the raw material being rich in carbon five carbon six alkane enters after catalytic dehydrogenating reaction device through preheating, and the olefin(e) centent in catalytic dehydrogenation product is not less than 35%.Under this proportioning raw materials, the yield of alkene is higher, and energy consumption is lower.
Further, dehydrogenation catalyst is made up of carrier and the first active ingredient, and carrier is the first high-temperature inorganic oxide and/or the first molecular sieve, and the first active ingredient is at least one of metal in VIB, VIII, IA and IIA race.This dehydrogenation catalyst has higher stability and catalytic activity, can promote the carrying out of dehydrogenation reaction further.
Further, the reaction conditions in catalytic dehydrogenating reaction device is: 450 ~ 700 DEG C, pressure 0.01 ~ 3MPa, and liquid volume air speed is 0.1 ~ 10h
-1.Under these processing condition, catalytic dehydrogenating reaction has higher speed of reaction and reaction conversion ratio.
Further, catalytic cracking catalyst comprises the second molecular sieve and one or more second active ingredients; Preferably, the second molecular screening is from ZSM-5, ZSM-8, ZSM-11, ZSM-38, Y type, ZRP, mordenite or SAPO molecular sieve; Preferably, the second active ingredient is at least one in IIB, III, VB, VIB, VIIB and group VIII metal; Preferably, containing the second high-temperature inorganic oxide in catalytic cracking catalyst, the second high-temperature inorganic oxide is selected from ZrO
2, Al
2o
3, SiO
2in one or several.Above-mentioned catalytic cracking catalyst has the catalytic activity of better stability and Geng Gao, is conducive to the speed of reaction and the reaction conversion ratio that improve catalytic cracking reaction further.
Further, the reaction conditions in catalytic cracking reaction device is: 450 ~ 650 DEG C, pressure 0.1 ~ 3.0MPa, and volume space velocity is 0.1 ~ 10h
-1.Under these processing condition, catalytic cracking reaction has higher speed of reaction and transformation efficiency.
Further, catalytic dehydrogenating reaction device, catalytic cracking reaction device are fixed-bed reactor; Preferably, catalytic dehydrogenating reaction device, catalytic cracking reaction device are that a reactor is used alone respectively, or cyclical operation is carried out in two or more reactor parallel connection use, or multiple reactor is in parallel and series combination uses.
Feature of the present invention is the raw material being rich in carbon five carbon six alkane to be converted into alkene through catalytic dehydrogenation, and carbon four mix after more further catalytic pyrolysis be converted into low-carbon alkene, lighter hydrocarbons low value-added for refinery can be changed into the ethylene, propylene of high additive value.Refinery C five carbon six alkane is through dehydrogenation, after the cracking of C_4 hydrocarbon mixed catalytic, generate ethylene, propylene, yield of ethene can reach 10% ~ 20%, propene yield reaches 20% ~ 50%, diene yield reaches 40% ~ 60%, olefin conversion reaches 80% ~ 90%, the present invention adopts and generates a large amount of alkene by after first for the raw material being rich in carbon five carbon six alkane dehydrogenation, the producing ethene, propylene through catalytic cracking through alkene is mixed again with C_4 hydrocarbon raw material, owing to containing at least one double bond in alkene composition, the alkane that its chemical property comparatively only has singly-bound to form wants active a lot, in catalytic pyrolysis process, required temperature of reaction is low, and ethylene, propylene yield is high.Therefore dehydrogenating technology process energy consumption is less again to adopt the more first cracking of technological process of catalytic pyrolysis after first dehydrogenation.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure: 1-catalytic dehydrogenating reaction device, 2-catalytic cracking reaction device, 3-separation system.
Embodiment
Below by embodiment in detail the present invention is described in detail.Table 1 ~ table 5 embodiment adopt the character of raw material, wherein raw material A is circulating water plant of Dushanzi Refinery reforming topped oil, raw material B is circulating water plant of Dushanzi Refinery hydrocracking light naphthar, raw material C is circulating water plant of Dushanzi Refinery aromatic hydrocarbons pentane oil, raw material D is Lanzhou Petrochemical Company catalysis workshop mixed c 4, and raw material E is that Daqing Refinery company one heavily urges mixed c 4." W% " represents mass percent.Table 6 is depicted as embodiment and comparative example experimental result.
Table 1 raw material A composition (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 3.19 | 5.20 | |||
| C 5 | 14.85 | 15.88 | 9.11 | 0.03 | |
| C 6 | 4.19 | 41.20 | 3.93 | 1.90 | |
| C 7 | 0.05 | 0.09 | 0.06 | ||
| C 8 | 0.16 |
Table 2 raw material B forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Aromatic hydrocarbons |
| C 4 | 5.81 | 8.82 | ||
| C 5 | 0.92 | 50.87 | 14.47 | |
| C 6 | 1.75 | 15.47 | 1.38 | 0.11 |
| C 7 | 0.12 | 0.22 | 0.01 | |
| C 8 | 0.05 |
Table 3 raw material C forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene |
| C 4 | 0.24 | 11.73 | 0.07 | |
| C 5 | 0.32 | 53.16 | 32.36 | 0.86 |
Table 4 raw material D forms (W%)
| Component | ω％ | Component | ω％ |
| Propane | 0.04 | Iso-butylene | 17.11 |
| Propylene | 0.01 | Cis-butene-2 | 12.51 |
| Trimethylmethane | 29.50 | Iso-pentane | 0.66 |
| Normal butane | 9.16 | 1,3-butadiene | 0.09 |
| Trans-butene-2 | 17.51 | 2-methyl-2-butene | 0.01 |
| 1-butylene | 13.39 | 1-amylene | 0.01 |
Table 5 raw material E forms
| Component | ω％ | Component | ω％ |
| Propane | 0.00 | Iso-butylene | 12.45 |
| Propylene | 0.00 | Cis-butene-2 | 12.79 |
| Trimethylmethane | 34.29 | Iso-pentane | 0.06 |
| Normal butane | 10.38 | 1,3-butadiene | 0.07 |
| Trans-butene-2 | 17.33 | 2-methyl-2-butene | 0.02 |
| 1-butylene | 12.63 | 1-amylene | 0.04 |
Embodiment all adopts technique as shown in Figure 1, and reactor all adopts 200ml fixed bed reactor.Embodiment 1 ~ 3 is single reactor periodical operation for catalytic dehydrogenating reaction device and catalytic cracking reaction device, and in embodiment 4 ~ 6, catalytic dehydrogenating reaction device and catalytic cracking reaction device are two reactor parallel circulatings and use.Analytic sample is the instantaneous sample of reaction after 10 hours.
Embodiment 1
Dehydrogenation catalyst adopts Haitai company HTPB-DH dehydrogenation catalyst, wherein with Al
2o
3for carrier with Pt and Cl for active ingredient, wherein the mass content of Pt is 1%, and chlorine mass content is 2%, and specific surface area is 200m
2/ g, pore volume 0.5ml/g, diameter is 1.59mm, bulk density 0.6g/cm
3.
Catalytic cracking catalyst adopts the method preparation of CN101045212A Catalyst Preparation Example 1, its concrete preparation process is as follows: get 284 grams of Starsos, be dissolved into solution A with 300 grams of distilled water, get 33.3 grams of Tai-Ace S 150, make solution B with 100 grams of distilled water, B solution is slowly poured in solution A, strong stirring, then adds 24.4 grams of quadrols, under stirring, by dilute sulphuric acid adjust ph 11.5, the mol ratio controlling colloidal sol is: Si ︰ A1 ︰ Yi bis-An ︰ H
20=1 ︰ 0.1 ︰ 0.4 ︰ 40, mixing solutions is put into autoclave, 180 DEG C of insulations 40 hours, then washing, oven dry, roasting is taken out, the composite molecular screen of obtained ZSM-5 and mordenite, with in the quantitative known composite molecular screen of XRD diffraction containing the mordenite of the ZSM-5 and 14.5% (weight) of 85.5% (weight).Be the ammonium nitrate solution of 5% by concentration, exchange twice at 70 DEG C, then roasting, after repeating twice, obtain hydrogen type molecular sieve, then compressing tablet, break into pieces, sieve, get 20-40 object particle.
Use raw material A and raw material D, the reaction conditions of catalytic dehydrogenation is temperature of reaction 480 DEG C, volume space velocity 0.1h
-1, reaction pressure 0.01MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 37.1%.The reaction conditions of catalytic cracking is: temperature of reaction 450 DEG C, volume space velocity 1.0h
-1, reaction pressure 0.5MPa, carbon four is 0.1:1 with the ratio of carbon five carbon six raw material, and products therefrom character is as shown in table 6.
Embodiment 2
The load 10%MoO that dehydrogenation catalyst adopts fine chemistry industry key lab of Xinjiang University to provide
3γ-Al
2o
3catalyzer, its preparation process takes a certain amount of (NH
4)
6mo
7o
244H
2o is dissolved in after in hot water and floods γ-Al
2o
3, stirring is evaporated to dry, dry 10h at 120 DEG C, finally roasting 4h at 550 DEG C, obtained catalyzer.
Catalytic cracking catalyst adopts the method preparation of CN1676499A catalyst preparing example 4, and concrete steps are as follows: (provided by economic technology trade center, Garden of Ten-Thousand Trees, Beijing, SiO by 45gZRP molecular sieve
2/ Al
2o
3> 200), 45g silicon oxide (specific surface area >200m
2the high-purity silicon oxide of/g), 50g zirconium white and 2g sesbania powder mixing, the nitric acid 80m1 of 5% is added after mixing, 2mm cylindrical type is squeezed into after stirring evenly, and cut into 2-3mm, 80 DEG C and 120 DEG C dry 10 hours respectively, then 580 DEG C of calcination 6 hours, take out and be cooled to room temperature, put into moisture eliminator for subsequent use.
Adopt raw material B and raw material D, the reaction conditions changing catalytic dehydrogenation is temperature of reaction 520 DEG C, volume space velocity 1.0h
-1, reaction pressure 1.0MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 51.6%.The reaction conditions changing catalytic pyrolysis is temperature of reaction 500 DEG C, volume space velocity 2h
-1, reaction pressure 0.5MPa, carbon four is 1:1 with the ratio of carbon five carbon six raw material, and products therefrom character is as shown in table 6.
Comparative example 1
Other condition is identical with embodiment 2, and difference is not add mixed c 4 raw material, and raw material B catalysis dehydrogenation is carried out catalytic pyrolysis, and products therefrom character is as shown in table 6.
Embodiment 3
Dehydrogenation catalyst adopts the method preparation of embodiment 1 in patent CN101618319A.2.24 grams of calcium oxide and 3.1 grams of polyoxyethylene glycol are dissolved in 120ml deionized water, 240 DEG C of hydrothermal treatment consists 24 hours, 600 DEG C of calcinations are after 5 hours, it is mixed with 7.2 grams of chromium nitrates, 6 grams of aluminium sesquioxides with appropriate dehydrated alcohol, after dry 12 hours, evenly, at 550 DEG C, calcination is for subsequent use after 3 hours in grinding.
Catalytic cracking catalyst adopts the method preparation of CN1927785A catalyst preparing example 1, concrete steps are as follows: the NaZSM-5 molecular sieve of 100 grams of moles of silica alumina ratios 200, first 600 DEG C of roastings, 4 hours Template removals under nitrogen flowing, with 0.1M, hydrochloric acid 1 liter 80 DEG C is exchanged three to four times again, with deionized water wash extremely without chlorine root, 120 DEG C of dry for standby.By 30 grams, above-mentioned molecular sieve with containing Ce
2o
3the cerous nitrate solution 50 milliliters of 2.08 grams is under agitation heated to dry up, and then dries 10 hours for 120 DEG C, 550 DEG C of roastings 2 hours, join the solution that 0.86 gram of 85% phosphoric acid and 30 grams of water are made into again, mix rear evaporate to dryness, dry 10 hours for 120 DEG C, 550 DEG C of roastings 2 hours are also pulverized.After mixing with 3 grams of sesbania powder, then add the dry pasty state of silicon sol furnishing of 50 gram 40%, and after suitably dewatering, extrusion is configured as Φ 1.6.After drying 10 hours at 120 DEG C, 550 DEG C of roastings obtain catalyzer in 4 hours.
Adopt raw material C and raw material D, the reaction conditions changing catalytic dehydrogenation is temperature of reaction 570 DEG C, volume space velocity 3.0h
-1, reaction pressure 1.5MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 54.9%.The reaction conditions changing catalytic pyrolysis is temperature of reaction 520 DEG C, volume space velocity 3h
-1, reaction pressure 0.1MPa.Carbon four is 2.5:1 with the ratio of carbon five carbon six raw material, and products therefrom character is as shown in table 6.
Comparative example 2
Other condition is identical with embodiment 3, difference be carbon four raw material not in the charging of catalytic cracking reaction device but from dehydrogenation reactor with carbon five carbon six raw material mixing rear feeding, carbon four is 2.5:1 with the ratio of carbon five carbon six raw material.Products therefrom character is as shown in table 6.
Embodiment 4
The method preparation of embodiment 4 in dehydrogenation catalyst CN101940922A.Its concrete steps are: the chromic oxide first taking 117.5 grams, is dissolved in deionized water and fully stirs, and being mixed with weight concentration is 47% chromic oxide solution.Configuration weight concentration be the Alkitrate of 3.86%.Then by 55.0 grams of pseudo-boehmites, 2.2 grams of wilkinites, the chromic oxide solution prepared with 7.59 grams fully mixes, and mediates, is extruded into bead.And then at 120 DEG C dry 3 hours, and then 500 DEG C of constant temperature 3 hours, 620 DEG C of constant temperature 2 hours, finally 760 DEG C of roastings 4 hours under 20% water and 80% air.Getting the chromic oxide solution 11.39 grams prepared again, flooding 20 minutes by joining burned sample, 120 DEG C of dryings 3 hours, 550 DEG C of constant temperature calcinings 5 hours.Get the Alkitrate dipping prepared again, 120 DEG C of dryings 3 hours, for subsequent use 620 DEG C of constant temperature calcinings 6 hours.
Catalytic cracking catalyst adopts the method preparation of CN1903808A Catalyst Preparation Example 2, concrete steps are as follows: get 1.38 grams of phosphoric acid (chemical pure, Beijing Yi Li Chemical Company produces) be dissolved in 53 ml deionized water, heated and stirred, to dissolving completely, filters rear saturated dipping 50 grams of ZSM-5 zeolites (Shandong catalyst plant is produced, trade mark ZRP), 110 DEG C of dryings 3 hours, 500 DEG C of roastings 2 hours, obtain the ZSM-5 of zinc modification, wherein P
2o
5content is 1.0%, and in 340 ml deionized water, adding 235 grams of pseudo-boehmites, (Shandong catalyst plant is produced, Al
2o
3content is 32 quality %), 90 DEG C are stirred to evenly, make the slurries that solid content is 15.0 quality %.The ZSM-5 getting 50 grams of above-mentioned P Modification is dissolved in 100 ml deionized water, makes the homogeneous slurry that solid content is 50 quality %.Get the half of 340 grams of above-mentioned pseudo-boehmite slurries, add appropriate 1:l hydrochloric acid wherein, adjustment slurry pH value is 2:3, stir the ZSM-5 slurries adding the P Modification of above-mentioned preparation after 30 minutes, stir 30 minutes, then add remaining half pseudo-boehmite dress liquid, stir 30 minutes, add Alumina gel (production of Shandong catalyst plant, the Al of 0.1 times of phosphorous modified ZSM-5 zeolite quality
2o
3content is 22 quality %).60 DEG C of stirrings added appropriate decationizing water after 40 minutes, obtained the catalyst pulp that solid content is 20 quality %.Wherein in solids, phosphorous modified ZSM-5 content is 50 quality %, Al
2o
3content is 50 quality %.Finally get catalyst pulp 500 grams, apply 200 holes/time
2, 120 DEG C of dryings 5 hours, 500 DEG C of roastings 2 hours, obtain ordered structure catalyst.
Adopt raw material A and raw material E, the reaction conditions changing catalytic dehydrogenation is temperature of reaction 600 DEG C, volume space velocity 5.0h
-1, reaction pressure 2.0MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 64.0%.The reaction conditions changing catalytic pyrolysis is temperature of reaction 550 DEG C, volume space velocity 6h
-1, reaction pressure 2MPa.Carbon four is 10:1 with the ratio of carbon five carbon six raw material, and products therefrom character is as shown in table 6.
Comparative example 3
Other condition is identical with embodiment 4, difference be carbon four raw material not in the charging of catalytic cracking reaction device but from dehydrogenation reactor with carbon five carbon six raw material mixing rear feeding, carbon four is 10:1 with the ratio of carbon five carbon six raw material.Products therefrom character is as shown in table 6.
Embodiment 5
Dehydrogenation catalyst adopts the method preparation of embodiment 9 in patent CN96121452.X.Take 17 grams of Cr (NO
3)
39H
2o, 1.1 grams of Cu (NO
3)
23H
2o, 80.8 grams of Al (NO
3)
3˙ 9H
2o, uses coprecipitation method Kaolinite Preparation of Catalyst, and KOH (or NaOH) solution of 10% selected by precipitation agent, nitrate is dissolved in distilled water, add precipitation agent while stirring, make it be fully formed gel, and pH value is 8.5 ~ 9, aging 3 hours, filter, at 110 DEG C, dry 20 hours, 650 DEG C of roastings 7 hours, for subsequent use after crushing and screening.
Catalytic cracking catalyst is according to the preparation method of catalyzer in embodiment in patent CN101703943A 1.Concrete steps are as follows: 10gZRP-1 molecular sieve (being labeled as A) is immersed in 15g containing in the aqueous solution of Yttrium trinitrate, fully mix, flood after 8 hours, remaining solution is evaporated by Rotary Evaporators at 80 DEG C of temperature.120 DEG C of dried overnight, then catalyzer is placed in retort furnace and is warming up to 700 DEG C, roasting 4 hours.Taking-up is cooled to room temperature, puts into moisture eliminator for subsequent use in mortar after grinding powder.The catalyst obtained, yttria levels is 0.3wt%.
Adopt raw material B and raw material E, the reaction conditions changing catalytic dehydrogenation is temperature of reaction 700 DEG C, volume space velocity 8.0h
-1, reaction pressure 3.0MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 35.6%.The reaction conditions of catalytic pyrolysis is temperature of reaction 600 DEG C, volume space velocity 8h
-1, reaction pressure 3.0MPa.Carbon four is 8:1 with the ratio of carbon five carbon six raw material, and products therefrom character is as shown in table 6.
Embodiment 6
Dehydrogenation catalyst adopts the step Kaolinite Preparation of Catalyst of catalyst preparing in embodiment 1 in patent CN101623633A.First the former powder of ZSM-5 molecular sieve is at the SnCl of carrier at 0.16M
22H
2in 80 DEG C of dipping 10hr in O solution, the charge capacity of the Sn in catalyzer is made to reach 4wt%, and then dry 6h at 120 DEG C.Dried sample is roasting 4hr under 550 DEG C of air atmosphere.Powder after roasting is at the H of 0.03M
2ptCl
66H
2at 80 DEG C, flood 4h in O solution, make finally to obtain the catalyzer that Pt content is 20wt%, then dry 6h at 120 DEG C, roasting 4h at 550 DEG C.After for subsequent use at 550 DEG C of hydrogen reducing 12h.
Catalytic cracking catalyst adopts the method preparation of catalyst preparing in embodiment 15 in patent CN1676213A.Concrete preparation process is: by the ZrOC1 of 0.2 mol/L
2(Solution on Chemical Reagents in Shanghai company produces, analytical pure) aqueous solution drops to (Beijing Chemical Plant produces, the heavy % of concentration 25) in the ammonia soln of 0.5 mol/L with continuous stirring, and the pH value controlling suspension is 11.The throw out obtained 25 DEG C stir under aging 5 hours, filtration under diminished pressure Zr0 (OH)
2gel, and with in deionized water wash to washing lotion without Cl
-1.By the ZrO (OH) after washing
2gel is poured in dehydrated alcohol, and the amount of ethanol is every gram of ZrO (OH)
2gel 10 milliliters, rapid stirring mixture 4 hours, filters and obtains ZrO (OH)
2alcogel.N
2in air-flow, rise to 110 DEG C of dryings 4 hours with the speed of 5 DEG C/min, within 6 hours, obtain ZrO to 600 DEG C of roastings
2powder.Obtained ZrO
2average crystal grain particle diameter is 50 nanometers.Get this ZrO
210 grams, powder, adds the lubricant sesbania powder of 0.05 gram, fully extrusion after mixing, and pelletizing, makes the bar shaped particle of 400-600 micron, as carrier.Get 0.4 gram of La (NO
3)
36H
2o (analytical pure) is made into the aqueous solution of 25 milliliters, and leave standstill with the carrier of solution impregnation 10 grams, dry in the shade, solid 120 DEG C of dryings 8 hours, 550 DEG C roastings 6 hours obtained catalyzer after flooding, containing the WO of 5.7 quality % in catalyzer
3, the La of 2.9 quality %
2o
3, all the other are ZrO
2.
Adopt raw material C and raw material E, the reaction conditions changing catalytic dehydrogenation is temperature of reaction 650 DEG C, volume space velocity 10.0h
-1, reaction pressure 0.15MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 44.7%.The reaction conditions of catalytic pyrolysis is: temperature of reaction 650 DEG C, volume space velocity 6h
-1, reaction pressure 0.5MPa, carbon four is 4:1 with the ratio of carbon five carbon six raw material.Products therefrom character is as shown in table 6.
Comparative example 4
Other condition is identical with embodiment 6, and difference is not add mixed c 4 in raw material, and raw material C is directly carried out catalysis dehydrogenation cracking, and products therefrom character is as shown in table 6.
Table 6 embodiment and comparative example experimental result
| Project | Ethylene yield/% | Productivity of propylene/% | Diene productive rate/% | Olefin conversion/% |
| Embodiment 1 | 8.64 | 26.51 | 35.15 | 82.88 |
| Embodiment 2 | 8.42 | 29.45 | 37.87 | 84.99 |
| Comparative example 1 | 6.83 | 22.75 | 29.58 | 74.54 |
| Embodiment 3 | 9.12 | 34.25 | 43.37 | 88.77 |
| Comparative example 2 | 8.15 | 32.46 | 40.61 | 84.34 |
| Embodiment 4 | 12.01 | 34.21 | 46.22 | 87.96 |
| Comparative example 3 | 8.08 | 31.31 | 39.39 | 82..35 |
| Embodiment 5 | 14.15 | 30.21 | 44.36 | 86.39 |
| Embodiment 6 | 13.54 | 29.74 | 43.28 | 86.36 |
| Comparative example 4 | 7.84 | 24.25 | 32.09 | 77.51 |
By example and comparative example visible, join after in raw material when there being mixed c 4, because catalytic pyrolysis proportioning raw materials changes, achieve beyond thought effect, not containing carbon four raw material in comparative example 1,4 Raw, ethylene, propylene productive rate is starkly lower than example and adds the rear catalytic pyrolysis effect of carbon four, and diene productive rate can differ from 10 percentage points at most.In addition from comparative example 2,3, when carbon four raw material enters catalyst cracking unit after dehydrogenation, more direct to enter reactive system diene productive rate from dehydrogenation unit higher.
Claims (15)
1. produce the method for ethylene, propylene for one kind, it is characterized in that, enter catalytic dehydrogenating reaction device after being rich in the raw material preheating of carbon five carbon six alkane to contact with catalytic dehydrogenation catalyst and carry out catalytic dehydrogenating reaction, catalytic dehydrogenation product and carbon four raw material are mixed into catalytic cracking reaction device and contact with catalytic cracking catalyst and carry out catalytic cracking reaction, catalytic cracking reaction products enters separation system and is separated into dry gas, ethene, propylene, liquefied gas, carbon four C 5 alkane, pyrolysis gasoline component and cracking masout component.
2. method according to claim 1, is characterized in that, the mass ratio of described carbon four raw material and carbon five carbon six paraffinic feedstock is 0.1:1 ~ 10:1; Preferably, described in be rich in after carbon five carbon six paraffinic feedstock enters catalytic dehydrogenating reaction device after preheating, in catalytic dehydrogenation product, olefin(e) centent is not less than 35%.
3. method according to claim 1, it is characterized in that, described dehydrogenation catalyst is made up of carrier and active ingredient, carrier is high-temperature inorganic oxide, or be the mixture of molecular sieve or molecular sieve and high-temperature inorganic oxide, active ingredient is for containing at least one metal in VIB, VIII, IA, IIA race.
4. method according to claim 1, is characterized in that, the reaction conditions in described catalytic dehydrogenating reaction device is: 450 ~ 700 DEG C, pressure 0.01 ~ 3MPa, and liquid volume air speed is 0.1 ~ 10h
-1.
5. method according to claim 1, is characterized in that, described catalytic cracking catalyst comprises molecular sieve and one or more active ingredients; Preferably, described molecular screening is from ZSM-5, ZSM-8, ZSM-11, ZSM-38, Y type, ZRP, mordenite, SAPO molecular sieve; Preferably, described active ingredient is the metal that at least one is selected from periodictable IIB, III, VB, VIB, VIIB and VIII; Preferably, containing high-temperature inorganic oxide in described catalytic cracking catalyst, ZrO is selected from
2, Al
2o
3, SiO
2in one or several.
6. method according to claim 1, is characterized in that, the reaction conditions in described catalytic cracking reaction device is: 450 ~ 650 DEG C, pressure 0.1 ~ 3.0MPa, and volume space velocity is 0.1 ~ 10h
-1.
7. method according to claim 1, is characterized in that, described catalytic dehydrogenating reaction device, catalytic cracking reaction device are fixed-bed reactor; Preferably, described catalytic dehydrogenating reaction device, catalytic cracking reaction device are that a reactor is used alone respectively, or cyclical operation is carried out in two or more reactor parallel connection use, or multiple reactor is in parallel and series combination uses.
8. produce a method for ethylene, propylene, it is characterized in that, said method comprising the steps of:
By be rich in carbon five carbon six alkane raw material preheating after, enter catalytic dehydrogenating reaction device and carry out catalytic dehydrogenating reaction, obtain catalytic dehydrogenation product;
After described catalytic dehydrogenation product is mixed with carbon four raw material, enter catalytic cracking reaction device and carry out catalytic cracking reaction and obtain catalytic cracking reaction products; And
Make described catalytic cracking reaction products enter separation system, be separated into dry gas, ethene, propylene, liquefied gas, carbon four C 5 alkane, pyrolysis gasoline component and cracking masout component.
9. method according to claim 8, is characterized in that,
After the described raw material being rich in carbon five carbon six alkane is carried out preheating, the raw material being rich in carbon five carbon six alkane described in after making preheating contacts with catalytic dehydrogenation catalyst and carries out described catalytic dehydrogenating reaction in described catalytic dehydrogenating reaction device, obtains described catalytic dehydrogenation product;
After described catalytic dehydrogenation product is mixed with described carbon four raw material, make compound enter described catalytic cracking reaction device and contact with catalytic cracking catalyst and carry out described catalytic cracking reaction, obtain described catalytic cracking reaction products.
10. method according to claim 8 or claim 9, it is characterized in that, described carbon four raw material and the described mass ratio being rich in carbon five carbon six paraffinic feedstock are 0.1:1 ~ 10:1; Preferably, described in be rich in carbon five carbon six alkane raw material enter after described catalytic dehydrogenating reaction device through preheating, the olefin(e) centent in described catalytic dehydrogenation product is not less than 35%.
11. methods according to claim 8 or claim 9, it is characterized in that, described dehydrogenation catalyst is made up of carrier and the first active ingredient, described carrier is the first high-temperature inorganic oxide and/or the first molecular sieve, and described first active ingredient is at least one of metal in VIB, VIII, IA and IIA race.
12. methods according to claim 8 or claim 9, it is characterized in that, the reaction conditions in described catalytic dehydrogenating reaction device is: 450 ~ 700 DEG C, pressure 0.01 ~ 3MPa, and liquid volume air speed is 0.1 ~ 10h
-1.
13. methods according to claim 8 or claim 9, is characterized in that, described catalytic cracking catalyst comprises the second molecular sieve and one or more second active ingredients; Preferably, described second molecular screening is from ZSM-5, ZSM-8, ZSM-11, ZSM-38, Y type, ZRP, mordenite or SAPO molecular sieve; Preferably, described second active ingredient is at least one in IIB, III, VB, VIB, VIIB and group VIII metal; Preferably, containing the second high-temperature inorganic oxide in described catalytic cracking catalyst, described second high-temperature inorganic oxide is selected from ZrO
2, Al
2o
3, SiO
2in one or several.
14. methods according to claim 8 or claim 9, it is characterized in that, the reaction conditions in described catalytic cracking reaction device is: 450 ~ 650 DEG C, pressure 0.1 ~ 3.0MPa, and volume space velocity is 0.1 ~ 10h
-1.
15. methods according to claim 8 or claim 9, it is characterized in that, described catalytic dehydrogenating reaction device, described catalytic cracking reaction device are fixed-bed reactor; Preferably, described catalytic dehydrogenating reaction device, described catalytic cracking reaction device are that a reactor is used alone respectively, or cyclical operation is carried out in two or more reactor parallel connection use, or multiple reactor is in parallel and series combination uses.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085145A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Process for producing ethylene and propylene by mixing C five-carbon hexaalkane and C four |
| CN114907178A (en) * | 2021-02-07 | 2022-08-16 | 中国石油天然气股份有限公司 | Method for producing C2-C3 olefin and high-octane gasoline blending component by using C4-C6 hydrocarbon as raw material |
| CN115888797A (en) * | 2022-11-08 | 2023-04-04 | 洛阳市科创石化科技开发有限公司 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
-
2015
- 2015-04-30 CN CN201510219120.5A patent/CN105085143A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085145A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Process for producing ethylene and propylene by mixing C five-carbon hexaalkane and C four |
| CN114907178A (en) * | 2021-02-07 | 2022-08-16 | 中国石油天然气股份有限公司 | Method for producing C2-C3 olefin and high-octane gasoline blending component by using C4-C6 hydrocarbon as raw material |
| CN115888797A (en) * | 2022-11-08 | 2023-04-04 | 洛阳市科创石化科技开发有限公司 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
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