CN102794195B - Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof - Google Patents
Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof Download PDFInfo
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- CN102794195B CN102794195B CN201210310661.5A CN201210310661A CN102794195B CN 102794195 B CN102794195 B CN 102794195B CN 201210310661 A CN201210310661 A CN 201210310661A CN 102794195 B CN102794195 B CN 102794195B
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- octane number
- olefin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000003502 gasoline Substances 0.000 title claims abstract description 88
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 58
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000446 fuel Substances 0.000 title claims abstract description 44
- 230000002708 enhancing effect Effects 0.000 title abstract 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 16
- 239000003915 liquefied petroleum gas Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- -1 molecular sieve metal oxide Chemical class 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 17
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- 238000004939 coking Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 239000010457 zeolite Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000640882 Condea Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof, belonging to a catalyst containing a molecular sieve. The catalyst is prepared from the following raw materials in percentage by mass: 25-50% of aluminum trioxide hydrate on the basis of Al2O3, 1-5% of P on the basis of P2O5, 0.1-5% of rare-earth oxide on the basis of RE2O3 and 50-75% of modified shape-selective molecular sieve. The invention provides a catalyst with olefin aromatization function; the fuel treated by the catalyst has the advantages of high gasoline octane number, low olefin content, high gasoline yield and low dry gas yield; and the catalyst has the advantages of low coking tendency and long service life. The catalyst is suitable for aromatization modification of fuel C4 liquefied petroleum gas, and can lower the olefin content of the fuel; and the catalyst enhances the straight-run gasoline octane number, and lowers the catalytically cracked gasoline olefin content. The C4 liquefied petroleum gas and the straight-run gasoline can be used as raw materials to produce modified fuel gasoline; and etherified C4 and straight-run naphtha can be used as raw materials to produce modified fuel gasoline.
Description
Technical field
The present invention is a kind of catalyst and application thereof that fuel gasoline octane number reduces its olefin(e) centent simultaneously that be applicable to improve.Belong to the catalyst that comprises molecular sieve.
Background technology
In state's III gasoline car discharge standard regulation gasoline, olefin(e) centent can not be higher than 30%, and arene content can not be high with 40%, and benzene content can not be high with 1%.At present, in fuel gasoline, catalytically cracked gasoline also claims olefin gasolines to occupy the larger market share, and its olefin(e) centent is higher, is difficult to meet the specification requirement of new standard.Especially the fuel gasoline that the crude oil catalytic cracking process that heavy oil and slag-mixing amount are very high is produced, olefin(e) centent is higher, depends merely on and improves catalytic cracking process technology, and olefin(e) centent is difficult to reach set quota.Therefore the olefin(e) centent, reducing in fuel gasoline becomes each refinery difficult problem anxious to be resolved.
The method of the olefin(e) centent in traditional reduction fuel gasoline has catalytic reforming, light petrol isomerization and the hydrocracking etc. of naphtha.These square law devices are complicated, invest larger.
In the catalytically cracked gasoline exceeding standard at olefin(e) centent, blending part direct steaming gasoline, the object that reaches its olefin(e) centent of reduction is the conventional methods of people.But the octane number of direct steaming gasoline is very low, mix the significantly decline that causes octane number in catalytically cracked gasoline, attend to one thing and lose sight of another, be difficult to make the best of both worlds.
Therefore, direct steaming gasoline is carried out to upgrading, improve after its octane number.Being re-used as blending modified component, joining in catalytically cracked gasoline, in order to reduce the olefin(e) centent of catalytically cracked gasoline, is desirable.
Certainly, directly catalytically cracked gasoline is converted into the fuel gasoline that octane number high olefin content is low, be the target that people pursue always.
No matter the raising upgrading of octane number of direct distillation gasoline, still passes through C
4olefin oligomerization or superimposed its olefin(e) centent that reduces improve its octane number simultaneously, and a kind of catalyst of applicable application is vital factor.
USP 3960978 proposes on the ZSM-5 zeolite of Controlled acidity, and gas alkene is converted into the olefin gasolines component of higher octane, and it is that ZSM-5 zeolite is carried out to ion-exchange, to replace the sodium ion in crystal, makes HZSM-5 zeolite.With nickel nitrate solution, mix again, compression molding, then at 105 ~ 200 ℃, dry 1 ~ 24 hour, in air, at 300 ~ 700 ℃, heat 1 ~ 18 hour, in order to control catalyst acidity, after compressing tablet, nickeliferous HZSM-5 zeolite need to be at 127 ~ 871 ℃, at best 538 ~ 816 ℃ by steam or part steam treatment, when this catalyst is used for alkene oligomerization, at weight space velocity 21.0h-1,427 ℃ of temperature, under 315 kilograms of pressure, by C3=total amount, be that 53% liquefied petroleum gas is raw material, unstable polymer gasoline yield is 37%.
CN 1013347B discloses a kind of zeolite catalyst preparation method for the superimposed production gasoline of alkene low pressure component.The method is pointed out to process with high-temperature steam, then, with potassium, sodium, calcium, magnesium slaine immersion treatment ZSM-5 zeolite catalyst, can significantly improve for activity and stability containing the superimposed catalyst of C2 ~ C5 olefin gas.The superimposed production gasoline component of catalytic cracking liquefied petroleum gas for catalyst prepared by this method, propylene conversion 79% left and right, turns round 29 days, and polymer gasoline component yield does not obviously decline, and polymer gasoline research octane number (RON) surpasses 90.
CN1080313A discloses a kind of catalytic modification of poor quality gasoline-aromatization method, and its catalyst is the rare earth modified HZSM-5 zeolite of Zn-Al or Zn-Al-, and to take aluminium oxide or silica be binding agent.This technology adopts two-part reaction unit, first order reactor makes raw material and catalyst haptoreaction under non-hydrogen, 300 ~ 550 ℃, the condition of 0.05 ~ 1.2MPa, weight (hourly) space velocity (WHSV) 0.2 ~ 10, reaction product is through gas-liquid separation, liquid discharge device aftercut more than C5, again the gasoline fraction obtaining is sent into second level reactor, under 0.05 ~ 1.5MPa, volume space velocity 20 ~ 2000,480 ~ 650 ℃ of conditions of bed temperature, carry out aromatization, reaction product obtains aromatic hydrocarbons mixture and the gas that is rich in hydrogen through gas-liquid separation.
CN 1212376C discloses a kind of lighter hydrocarbons non-hydrogen modifying catalyst and preparation method and application, the non-hydrogen modifying catalyst that relates to a kind of C3 ~ C11 mixture of light hydrocarbons, the carrier that comprises the mixed rare-earth oxide of 0.1 ~ 5.0 quality % or antimony oxide, 95.0 ~ 99.1 quality %, described carrier is comprised of the HZSM-5 zeolite of 50 ~ 80 quality % and the gama-alumina of 20 ~ 50 quality %.This catalyst is used in low octane rating gasoline modifying to improve octane number and to reduce olefin(e) centent.
CN 1651141A discloses a kind of aromatized catalyst and its preparation method and application, adopting ZSM-5 and the Y zeolite of modification is active component, modifying element is zinc, phosphorus and rare earth metal, Y molecular sieve is REY or high silicon Y, using aluminium colloidal sol or Ludox as binding agent, and by rolling moulding, making diameter is the pellet catalyst of 1.4 ~ 2.0 millimeters.This catalyst is applied to moving-burden bed reactor, can realize the continuous aromatization reaction of low octane value gasoline or naphtha.The sustainable comparatively stable product yield of the method and distribution, but react to such an extent that dry gas yied is still higher, and also plant investment is larger.
CN200410050202 discloses a kind of Catalysts and its preparation method of carbon four liquefied petroleum gas aromatisation, the parent of catalyst is the silica-rich zeolite of grain size 10 ~ 500 nanometers, to after described zeolite and aluminium oxide moulding, through ammonium, exchange and make hydrogen type catalyst, then hydrogen type catalyst is carried out to steam treatment and adjust its acidity, with sour reaming, recover again the smoothness in catalyst duct, acid used can be the inorganic acids such as hydrochloric acid, nitric acid or sulfuric acid, also can be the organic acids such as formic acid, acetic acid or citric acid.The aromatization that the standby catalyst of this legal system carries out at fixed bed reactors for carbon 4 liquid gas, can obtain the gasoline component compared with low olefin-content.
In sum, in prior art, be applicable to improve the following deficiency of catalyst existence that fuel gasoline octane number reduces its olefin(e) centent simultaneously:
1. device is complicated, invests larger.
2. improve octane number and reduce olefin(e) centent simultaneously, effect is not good enough.
3. dry gas yied is higher..
4. purposes is single, or is applicable to alkene aromatisation, or is applicable to improve octane number.
5. in use easily tie carbon, catalyst is short service life.
Summary of the invention
The object of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of, both had alkene aromatisation function and have and improve octane number function, fuel gasoline octane number after processing is high, olefin(e) centent is low; Fuel gasoline conversion ratio is high, dry gas yied supports; Be difficult for knot carbon, catalyst long service life; Manufacturing process is simple, excellent performance be applicable to improve catalyst and the application thereof that fuel gasoline octane number reduces its olefin(e) centent simultaneously.
Object of the present invention can reach by following measure:
Of the present invention being applicable to improved the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, it is characterized in that by making according to the raw material of mass fraction meter as follows:
Described modification shape-selective molecular sieve is that conventional crystallization sodium type ZSM-5 molecular sieve is exchanged and removed after sodium through ammonium, introducing is selected from a kind of in Ga, Mn, Zn metallic element to be carried out modification and obtains molecular sieve, and the silica alumina ratio of described crystallization sodium ZSM-5 molecular sieve is 20 ~ 300;
Its preparation method comprises the steps:
1. the preparation of phosphorus aluminium liquid
According to P
2o
5: Al
2o
3mole proportioning of=1 ~ 5:1, is dissolved in orthophosphoric acid and hydrated alumina respectively in deionized water, mixes and be modulated into the phosphorus aluminium glue of solid content 20～40wt/%, at ℃ temperature of room temperature ~ 60, stirs peptization 1 ~ 5 hour; Make described phosphorus aluminium liquid, standby;
2.. the preparation of carrier
Phosphorus aluminium liquid and alumina hydrate powder that 1. modification shape-selective molecular sieve, step are prepared mix in proportion, and adding volume ratio is 1:1 nitric acid, control nitric acid: carrier butt=1mL:100g; Add again water, control water: carrier butt=1:4; The mixed material that is made into is mediated agglomerating, in banded extruder, being squeezed into diameter is 2 millimeters, the bar of long 3-5 millimeter, and 100 ~ 150 ℃ are dried 5 ~ 15 hours, then roasting 1 ~ 8 hour at 500 ~ 600 ℃, make catalyst carrier, standby;
3. the preparation of catalyst precursor
The carrier that 2. step is prepared, with the aqueous solution of chlorination mishmetal in room temperature ~ 100 ℃ dipping 1 ~ 5 hour, wherein carrier butt: water: Re
2o
3=1:1:0.001 ~ 0.050 is dried 5 ~ 15 hours, then 500 ~ 600 ℃ of roastings 1 ~ 8 hour, obtains catalyst precursor at 100 ~ 150 ℃ of temperature;
4. the preparation of catalyst
The catalyst precursor that 3. step is prepared carries out hydrothermal calcine processing, 500 ~ 700 ℃ of sintering temperatures, roasting time 1 ~ 10 hour, total inflow: catalyst butt=1 ~ 10:1, makes catalyst prod.
The molecular sieve containing in the present invention has suitable acidity, under the effect of solid acid catalysis, makes the butylene in c4 fraction carry out oligomerisation and aromatization, a series of upgrading reactions such as direct steaming gasoline generation selective splitting, isomerization and aromatisation.The hydrogen that wherein direct steaming gasoline reaction generates can be directly used in the hydrogenation reaction of butene oligomerization thing, makes to generate isoparaffin.Catalyst, through modification and stable processing, has good carbon accumulation resisting ability, and catalyst single pass life is long.
Object of the present invention can also reach by following measure:
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, by making according to the raw material of mass fraction meter as follows:
It is preferred technical scheme.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, described hydrated alumina is selected from one or more in boehmite, boehmite, boehmite, gibbsite.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, described hydrated alumina is boehmite.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, the silica alumina ratio of described crystallization sodium ZSM-5 molecular sieve is 30～120.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, described modification shape-selective molecular sieve metal oxide content is 0.5 ~ 3.0wt%.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, described modification shape-selective molecular sieve metal oxide content is 0.82wt%.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, the modified metal element of described modification shape-selective molecular sieve is Ga.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, the source of described P is from orthophosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, polymer phosphate and corresponding salt thereof, to choose at least one or its any two or more combinations.
Of the present invention being applicable to improved the application that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously, it is characterized in that being applicable to:
1. fuel carbon four liquefied petroleum gas aromatisation modifications reduce olefin(e) centent simultaneously;
2. direct steaming gasoline is proposed high-octane raising;
3. the reduction of catalytic cracking gasoline olefine content;
4. take catalytically cracked gasoline and direct steaming gasoline mixture as raw material production modified fuel gasoline;
5. take carbon four liquefied petroleum gas and direct steaming gasoline as raw material production modified fuel gasoline;
6. the compound of carbon four and 50% straight-run naphtha after 50% ether of take is that raw material is produced modified fuel gasoline.
Of the present inventionly be applicable to improve the catalyst that fuel gasoline octane number reduces its olefin(e) centent simultaneously, have compared to existing technology following good effect:
1. provide a kind of and not only had alkene aromatisation function but also had the octane number of raising function, fuel gasoline octane number after processing is high, olefin(e) centent is low; Fuel gasoline conversion ratio is high, dry gas yied supports; Be difficult for knot carbon, the catalyst of catalyst long service life;
2. provide a kind of manufacturing process simple, excellent performance be applicable to improve the preparation method that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously.
3. the molecular sieve that catalyst of the present invention contains has suitable acidity, under the effect of solid acid catalysis, makes the butylene in c4 fraction carry out oligomerisation and aromatization, a series of upgrading reactions such as direct steaming gasoline generation selective splitting, isomerization and aromatisation.The hydrogen that wherein direct steaming gasoline reaction generates can be directly used in the hydrogenation reaction of butene oligomerization thing, makes to generate isoparaffin.
4. catalyst, through modification and stable processing, has good carbon accumulation resisting ability, and catalyst single pass life is long.
The specific embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
According to following method, prepare catalyst of the present invention
By 0.148Kg Ga
2(SO
4)
3wiring solution-forming is to 6.5Kg(dry basis) through ammonium, hand over washing (Na
2the heavy % of O<0.1) ammonium type ZSM-5 molecular sieve (silica alumina ratio 80) carries out room temperature incipient impregnation 2h, 120 ℃ of dry 12h then, 550 ℃ of roasting 2h.
By 0.093Kg(dry basis, lower with) phosphoric acid and the deionized water preparation solid content of boehmite (the heavy % of solid content 73.67, Shandong Aluminum Plant), the heavy % of 0.422Kg85 be the phosphorus aluminium glue of 30 weight %, at stirring at room peptization 2h.
Above modified zsm-5 zeolite and phosphorus aluminium glue and 3.41Kg α-mono-water alumina powder (German Condea company produce) are mixed, carrier butt=1mL:100g) and water (water: solution carrier butt=1:4) being made into add 1:1 nitric acid (nitric acid:, mediate agglomerating, in banded extruder, being squeezed into diameter is 2 millimeters, the bar of long 3-5 millimeter, 120 ℃ dry 12 hours, 550 ℃ of roastings 3 hours.
Get above-mentioned carrier, with 12.66Kg, contain 0.057KgRe
2o
3the aqueous solution of chlorination mishmetal 65 ℃ of dippings 2 hours, 120 ℃ dry 12 hours, 550 ℃ of roastings 4 hours.
The catalyst that above step is made carries out hydrothermal calcine processing, 570 ℃ of sintering temperatures, roasting time 4 hours, total inflow: catalyst butt=4:1.Finally obtain catalyst provided by the invention.
Embodiment 2
According to following method, prepare catalyst of the present invention
By 0.176KgMn (NO
3)
2wiring solution-forming is to 7Kg(dry basis) through ammonium, hand over washing (Na
2the heavy % of O<0.1) ammonium type ZSM-5 molecular sieve (silica alumina ratio 120) carries out room temperature incipient impregnation 2h, 120 ℃ of dry 12h then, 550 ℃ of roasting 2h.
By 0.11Kg(dry basis, lower with) phosphoric acid and the deionized water preparation solid content of boehmite (the heavy % of solid content 73.67, Shandong Aluminum Plant), the heavy % of 0.45Kg85 be the phosphorus aluminium glue of 30 heavy %, at 45 ℃ of stirring peptization 2h.
Above modified zsm-5 zeolite and phosphorus aluminium glue and 2.89Kg α-mono-water alumina powder (German Condea company produce) are mixed, carrier butt=1mL:100g) and water (water: solution carrier butt=1:4) being made into add 1:1 nitric acid (nitric acid:, mediate agglomerating, in banded extruder, being squeezed into diameter is 2 millimeters, the bar of long 3-5 millimeter, 120 ℃ dry 12 hours, 550 ℃ of roastings 3 hours.
Get above-mentioned carrier, with 13Kg, contain 0.13KgRe
2o
3the aqueous solution of chlorination mishmetal room temperature dipping 2 hours, 120 ℃ dry 12 hours, 550 ℃ of roastings 4 hours.
The catalyst that above step is made carries out hydrothermal calcine processing, 600 ℃ of sintering temperatures, roasting time 2 hours, total inflow: catalyst butt=2:1.Finally obtain catalyst provided by the invention.
Embodiment 3
According to following method, prepare catalyst of the present invention
By 0.14KgZn (NO
3)
2wiring solution-forming is to 6Kg(dry basis) through ammonium, hand over washing (Na
2the heavy % of O<0.1) ammonium type ZSM-5 molecular sieve (silica alumina ratio 50) carries out room temperature incipient impregnation 2h, 120 ℃ of dry 12h then, 550 ℃ of roasting 2h.
By 0.072Kg(dry basis, lower with) phosphoric acid and the deionized water preparation solid content of boehmite (the heavy % of solid content 73.67, Shandong Aluminum Plant), the heavy % of 0.39Kg85 be the phosphorus aluminium glue of 30 heavy %, at 60 ℃ of stirring peptization 2h.
Above modified zsm-5 zeolite and phosphorus aluminium glue and 3.93Kg α-mono-water alumina powder (German Condea company produce) are mixed, carrier butt=1mL:100g) and water (water: solution carrier butt=1:4) being made into add 1:1 nitric acid (nitric acid:, mediate agglomerating, in banded extruder, being squeezed into diameter is 2 millimeters, the bar of long 3-5 millimeter, 120 ℃ dry 12 hours, 550 ℃ of roastings 3 hours.
Get above-mentioned carrier, with 12Kg, contain 0.24KgRe
2o
3the aqueous solution of chlorination mishmetal 80 ℃ of dippings 2 hours, 120 ℃ dry 12 hours, 550 ℃ of roastings 4 hours.
The catalyst that above step is made carries out hydrothermal calcine processing, 550 ℃ of sintering temperatures, roasting time 6 hours, total inflow: catalyst butt=5:1.Finally obtain catalyst provided by the invention.
Comparative example
The catalyst of reference agent for preparing according to CN1212376C method.
Embodiment 4
The following examples illustrate the performance of catalyst provided by the invention.
The evaluation of catalyst performance is carried out on small fixed evaluating apparatus.The feedstock oil of evaluation experimental is carbon four after straight-run naphtha and ether, and feedstock property is listed in table 1 and table 2
Table 1 straight-run naphtha character
| Boiling range, ℃ | |
| Initial boiling point | 70 |
| 10％ | 91 |
| 30％ | 106 |
| 50％ | 120 |
| 70％ | 135 |
| 90％ | 155 |
| The end point of distillation | 170 |
| Group composition, quality % | |
| Alkane | 53.26 |
| Cycloalkane | 42.23 |
| Aromatic hydrocarbons | 4.51 |
| Octane number | |
| Motor method (MON) | 55.0 |
| Organon (RON) | 56.1 |
| Density (20 ℃), g/cm3 | 0.730 |
| Sulfur content, μ g/g | 8 |
| Nitrogen content, μ g/g | 0.9 |
After table 2 ether, carbon four forms
| Component | Form ω % |
| Propylene | 0.07 |
| Propane | 0.06 |
| Iso-butane | 43.51 |
| Isobutene | 0.40 |
| N-butene-1 | 12.57 |
| Normal butane | 6.75 |
| Anti-butene-2 | 18.48 |
| Maleic-2 | 18.06 |
| Water | 0.05 |
| Dimethyl ether | 0.05 |
| Methyl alcohol | ≤50ppm |
| MTBE | ≤50ppm |
In 20 milliliters of continuous flow reactor of fixed bed, load 20mL, 14.6g catalyst, the compound of carbon four and 50% straight-run naphtha after 50% ether of take is charging, 400 ℃ of bed temperatures, reaction pressure 0.3Mpa, charging mass space velocity 0.5h
-1conditions of non-hydrogen under carry out upgrading reaction, the results are shown in table 3.
Table 3 straight-run naphtha upgrading evaluation result
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Product forms, quality % | ||||
| Dry gas | 0.35 | 0.40 | 0.38 | 0.45 |
| Liquefied gas | 39.11 | 40.23 | 39.56 | 42.79 |
| C5+ gasoline fraction | 60.54 | 59.37 | 60.06 | 56.76 |
| Gasoline property | ||||
| Olefin(e) centent, volume % | 0.85 | 0.92 | 0.89 | 0.95 |
| BTX content, quality % | 19.36 | 18.92 | 19.01 | 18.05 |
| Total arene content, quality % | 28.53 | 28.18 | 28.32 | 27.65 |
| Motor octane number (MON) | 80.6 | 79.9 | 80.1 | 76.9 |
| Research octane number (RON) (RON) | 89.5 | 88.7 | 89.2 | 85.3 |
| Olefin(e) centent in liquefied gas, quality % | 3.1 | 3.5 | 3.4 | 4.2 |
From evaluation result, can find out, adopt catalyst provided by the invention, in straight-run naphtha, sneaking into 50% carbon four carries out after upgrading, gasoline fraction yield can reach more than 60%, alkene volumn concentration < 1% in gasoline, aromatic hydrocarbons quality percentage composition significantly increases, more than research octane number (RON) improves 32Ge unit, more than motor octane number improves Liao24Ge unit.Meanwhile, in the liquefied gas component that reaction produces, alkene quality percentage composition, lower than 5%, is high-quality liquefied gas, meets the quality standard of motor liquified gas.In course of reaction, dry gas yield < 1%, has good economy.Compare with comparative example, catalyst provided by the invention has higher yield of gasoline and the octane number of Geng Gao.
Embodiment 5
The life-span of the catalyst that the following examples explanation embodiment 1 provides.
In 30 milliliters of continuous flow reactor of fixed bed, load 30mL, 21.9g catalyst, the compound of carbon four and 50% straight-run naphtha after 50% ether of take carries out the single pass life test of upgrading reaction as charging, reaction pressure 0.3Mpa, charging mass space velocity 0.5h-1, under 350～420 ℃ of conditions of non-hydrogen of bed temperature, 42 days (1008 hours) are carried out in reaction altogether, and reaction result is listed in table 4.
Table 4 catalyst life evaluation result
| Reaction number of days | 1-4 | 5-9 | 10-16 | 17-23 | 24-31 | 32-38 | 39-42 |
| Bed temperature, ℃ | 350 | 370 | 380 | 390 | 400 | 410 | 420 |
| Average dry gas yied, quality % | 0.30 | 0.48 | 0.52 | 0.61 | 0.69 | 0.85 | 0.94 |
| Stable gasoline character | |||||||
| RON | 89.6 | 89.1 | 88.2 | 88.5 | 87.4 | 87.1 | 86.5 |
| MON | 81.2 | 80.5 | 79.3 | 79.8 | 78.5 | 77.9 | 77.5 |
| Olefin(e) centent, volume % | 0.94 | 0.89 | 1.1 | 1.0 | 1.2 | 0.99 | 1.1 |
| Arene content, quality % | 28.6 | 29.2 | 27.8 | 27.5 | 28.1 | 28.8 | 28.2 |
As can be seen from the table, catalyst was used after 1000 hours, and the research octane number (RON) of gained reformulated gasoline still can reach more than 85, and content of olefin in gasoline < 1.5% can reach the quality requirement of reformulated gasoline.
Claims (4)
1. be applicable to improve the application that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously, it is characterized in that described catalyst is by making according to the raw material of mass fraction meter as follows:
The summation of described catalyst raw material mass fraction is 100%;
Described modification shape-selective molecular sieve is that conventional crystallization sodium type ZSM-5 molecular sieve is exchanged and removed after sodium through ammonium, introducing is selected from a kind of in Ga, Mn, Zn metallic element to be carried out modification and obtains molecular sieve, and the silica alumina ratio of described crystallization sodium ZSM-5 molecular sieve is 30～120;
Described modification shape-selective molecular sieve metal oxide content is 0.5～3.0wt%;
Described hydrated alumina is selected from one or more in boehmite, boehmite, boehmite, gibbsite;
The source of described P is from orthophosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, polymer phosphate and corresponding salt thereof, to choose at least one or its any two or more combinations;
The preparation method of described catalyst comprises the steps:
1. the preparation of phosphorus aluminium liquid
According to P
2o
5: Al
2o
3mole proportioning of=1～5:1, is dissolved in orthophosphoric acid and hydrated alumina respectively in deionized water, mixes and be modulated into the phosphorus aluminium glue of solid content 20～40wt/%, at ℃ temperature of room temperature～60, stirs peptization 1～5 hour; Make described phosphorus aluminium liquid, standby;
2.. the preparation of carrier
Phosphorus aluminium liquid and alumina hydrate powder that 1. modification shape-selective molecular sieve, step are prepared mix in proportion, and adding volume ratio is 1:1 nitric acid, control nitric acid: carrier butt=1mL:100g; Add again water, control water: carrier butt=1:4; The mixed material that is made into is mediated agglomerating, in banded extruder, being squeezed into diameter is 2 millimeters, the bar of long 3～5 millimeters, 100～150 ℃ dry 5～15 hours, then roasting 1～8 hour at 500～600 ℃, makes catalyst carrier, standby;
3. the preparation of catalyst precursor
The carrier that 2. step is prepared, with the aqueous solution of chlorination mishmetal in room temperature～100 ℃ dipping 1～5 hour, wherein carrier butt: water: Re
2o
3=1:1:0.001～0.050 is dried 5～15 hours, then 500～600 ℃ of roastings 1～8 hour, obtains catalyst precursor at 100～150 ℃ of temperature;
4. the preparation of catalyst
The catalyst precursor that 3. step is prepared carries out hydrothermal calcine processing, 500～700 ℃ of sintering temperatures, roasting time 1～10 hour, total inflow: catalyst butt=1～10:1, makes catalyst prod;
Described catalyst is applicable to:
1. fuel carbon four liquefied petroleum gas aromatisation modifications reduce olefin(e) centent simultaneously;
2. the raising of octane number of direct distillation gasoline;
3. the reduction of catalytic cracking gasoline olefine content;
4. take catalytically cracked gasoline and direct steaming gasoline mixture as raw material production modified fuel gasoline;
5. take carbon four liquefied petroleum gas and direct steaming gasoline as raw material production modified fuel gasoline;
6. the compound of carbon four and 50% straight-run naphtha after 50% ether of take is that raw material is produced modified fuel gasoline.
According to claim 1 be applicable to improve the application that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously, it is characterized in that the hydrated alumina in the raw material of described catalyst is boehmite.
According to claim 1 be applicable to improve the application that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously, it is characterized in that the modification shape-selective molecular sieve metal oxide content in the raw material of described catalyst is 0.82wt%.
According to claim 1 be applicable to improve the application that fuel gasoline octane number reduces the catalyst of its olefin(e) centent simultaneously, it is characterized in that the modified metal element that the modification shape-selective molecular sieve in the raw material of described catalyst adopts is Ga.
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| CN107570203B (en) * | 2016-07-05 | 2020-05-19 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof |
| CN107583667B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
| CN107583668B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
| CN107583666B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
| CN107583670B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
| CN115261057A (en) * | 2022-07-17 | 2022-11-01 | 中国石油化工股份有限公司 | Method for directly producing olefin and aromatic hydrocarbon by catalytically cracking gasoline |
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