CN100473461C - Catalyst for C4 liquefied petroleum gas aromatization and preparing method thereof - Google Patents
Catalyst for C4 liquefied petroleum gas aromatization and preparing method thereof Download PDFInfo
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- CN100473461C CN100473461C CNB2004100502023A CN200410050202A CN100473461C CN 100473461 C CN100473461 C CN 100473461C CN B2004100502023 A CNB2004100502023 A CN B2004100502023A CN 200410050202 A CN200410050202 A CN 200410050202A CN 100473461 C CN100473461 C CN 100473461C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 157
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003915 liquefied petroleum gas Substances 0.000 title claims description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 102
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 99
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 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 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 22
- 150000001336 alkenes Chemical class 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003209 petroleum derivative Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 23
- 230000004048 modification Effects 0.000 description 23
- 239000007788 liquid Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000002841 Lewis acid Substances 0.000 description 20
- 239000003502 gasoline Substances 0.000 description 20
- 150000007517 lewis acids Chemical class 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 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 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- -1 C 4 olefin Chemical class 0.000 description 8
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 230000009849 deactivation Effects 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001723 mesolite Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003068 static effect Effects 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to the field of catalyst preparation in petrochemical technology, and especially one kind of catalyst for the aromatization of liquefied C4 petroleum gas in fixed bed reactor and its preparation process. Technologically, the catalyst features that its mother substance is high-silicon zeolite with crystal granulation of 10-500 nm and the zeolite is alumina formed and prepared into the hydrogen type catalyst via conventional process, and the hydrogen type catalyst is vapor treated to regulate the acidity and acid treated to expand the pores and restore the pore passage. The catalyst is used in the aromatization of liquefied C4 petroleum gas, and has low reaction temperature, high olefin converting rate and high carbon deposition resistance.
Description
Technical field
The invention belongs to the petrochemical catalyst preparing technical field.Relate to a kind of Catalysts and its preparation method that is applicable to carbon four liquefied petroleum gas aromatisation in fixed bed reactors.
Background technology
Carbon four liquefied petroleum gas that the steam cracking device of oil plant and various catalytic cracking unit by-product are a large amount of.Contain a large amount of various butylene in carbon four liquefied petroleum gas, it is a very significant utilization of resources approach that butylene is converted into fuel gasoline.
Patent documentation US3960978 (1976) disclosed a kind of can be with low-carbon alkene (C
2～C
5) being converted into the catalyst of olefin gasolines by oligomeric or superimposed approach, this catalyst belongs to Ni, Zn or the metal ion-modified ZSM-5/ZSM-11 of Cr.After this patent, the oligomeric or polymerization catalyst that many patents relate to low-carbon alkene appearred again both at home and abroad.Low-carbon alkene is converted into olefin gasolines by oligomeric or superimposed approach certain application limitation is arranged.This is because the content of alkene in gasoline has been subjected to strict restriction, so olefin gasolines just can be accepted after must hydrogenation saturated.And hydrogenation need increase equipment investment, particularly will consume hydrogen resource very in short supply.
On the other hand, by low-carbon alkene (C
2～C
5) aromatization can obtain aromatisation gasoline.The aromatization of low-carbon alkene comprises following main elementary reaction step: at first, low-carbon alkene in more weak Bronsted acid in the heart by oligomeric or superimposed generation long-chain olefin, isomery, cyclisation generate the aromatic hydrocarbons presoma to above-mentioned then long-chain olefin in the heart in stronger Bronsted acid, at last, the aromatic hydrocarbons presoma is sloughed hydrogen atom and is generated aromatic hydrocarbons on the Lewis acid centers (being L-acid) of moderate strength, then carried out addition reaction by the hydrogen atom sloughed, make two keys of alkene (comprising low-carbon alkene and the long-chain olefin by oligomeric or superimposed generation) saturated with two keys of alkene.Owing to have above-mentioned hydrogen transfer reaction in the aromatization process,, need not consume hydrogen again and carry out saturated so the olefin(e) centent in the aromatisation gasoline (referring to carbon five above liquid hydrocarbons) seldom.In the aromatisation gasoline except a large amount of high-octane aromatic components, also contain many saturated alkanes, wherein having quite a lot of is high-octane isoparaffin, therefore the aromatisation gasoline cost that obtains from low-carbon alkene is low, octane number is high, alkene and sulfur content are low, are good clean gasoline blend components.As previously mentioned, aromatization process is the process of a Bronsted acid center and Lewis acid centers concerted catalysis.Because the transfer of each hydrogen atom all needs just can finish by the fracture of a carbon-hydrogen link and the formation of a carbon-hydrogen link, and form an aromatic hydrocarbon molecule and need shift a plurality of hydrogen atoms, therefore the hydrogen migration step is the rate controlling step in the aromatization, and the quantity comparison aromatization at Lewis acid centers on the raising catalyst and Bronsted acid center is favourable.Usually, the Lewis acid centers on the aromatized catalyst must be regulated in catalyst modification with the quantity ratio at Bronsted acid center.In addition, owing to always have the carbon deposit process to follow generation in the aromatization process, so the coking deactivation problem of aromatized catalyst is all very outstanding.Causing one of reason of aromatized catalyst coking deactivation, is exactly to have strong acid center (comprising Bronsted acid center and Lewis acid centers) on the catalyst.Strong acid center can make reactant and product produce strong absorption, thereby accelerates the deactivation rate of catalyst.Therefore the strong acid center of eliminating catalyst is favourable to the reaction stability that improves catalyst.Usually, the strong acid center of eliminating on the aromatized catalyst also must be finished in catalyst modification.
Disclosed some low-carbon alkene aromatized catalysts and preparation method thereof in the following patent documentation:
The a kind of of US4150062 (1979) disclosure can use C
2～C 4 olefin is produced the zeolite catalyst of high-octane rating aromatic type gasoline, is metal ion-modified ZSM-5, ZSM-11, ZSM-12, ZSM-35 or ZSM-38 zeolite.Describe the aromatization effect of a kind of potassium modified ZSM-5 in fixed bed reactors in the embodiment in detail.Wherein, in order to reduce the carbon distribution deactivation rate of catalyst, this patent adopts water as co-fed (water/olefin molar ratio is 0.5～15).
The low-carbon alkene aromatized catalyst that CN1057476 (1992) discloses is to contain zinc ZSM zeolite catalyst.Describe a kind of Zn-Ti (SO in the embodiment in detail
4)
2The reaction effect of-ZSM-5 zeolite catalyst in fixed bed reactors: in raw liquefied petroleum gas charging air speed is that WHSV is 1～2h
-1, reaction temperature is under 500～550 ℃ the condition, altogether said catalyst has been carried out 1000 hours reaction evaluating.But, in 1000 hours reaction time, need regeneration 6 times altogether.In 168 hours one way reaction evaluating of one-time continuous reaction, the yield of benzene, toluene and dimethylbenzene (BTX) finally reduces to 32% from 42.0% of beginning in the product.
CN1154687 (1997) has disclosed the passivating modified ZSM-5 zeolite catalyst of a kind of water vapour.In the tower fixed bed single hop of two reactions adiabatic reactor, be raw material with C 4 mixture, be 2.8h at charging air speed WHSV
-1, pressure is 0.5Mpa, reaction temperature is under 530 ℃ the condition, C when reaction proceeds to 10 hours
6～C
9Aromatics yield has reached 52.3wt%, C during successive reaction to 120 hour
6～C
9Aromatics yield is reduced to 49wt%.
A kind of aromatized catalyst that CN1232071 (1999) discloses is with ZSM-5 zeolite and γ-Al
2O
3Be carrier, handle the catalyst of modification after Zn and the mishmetal modification again through steam.When being raw material with the mixed c 4, in fixed bed reactors, be 530 ℃ in reaction temperature, reaction pressure is 0.2MPa, charging air speed WHSV is 0.65h
-1Condition under, successive reaction 450 hours, the initial value of aromatics yield is 50wt%, finally reduces to 43wt%.
A kind of catalyst that CN1321728 (calendar year 2001) discloses is with ZSM-5 zeolite and γ-Al
2O
3Be carrier, obtain through steam processing modification again after Zn and the mishmetal modification.When charging is a liquefied petroleum gas, be reflected at normal pressure, 530-540 ℃, WHSV is 0.6 ± 0.1h
-1Carried out continuously 16 days under the condition, the conversion ratio of reaction active princlple and the initial value of aromatics yield are respectively 85% and 40%, and end value is respectively 68% and 38%.
A kind of aromatized catalyst that CN1340601 (2002) discloses, it is characterized in that, be parent with the ZSM-5 zeolite, first impregnating metal ion (Zn), introduce the second modification component VA or group vib metal again preventing the loss of Zn, it is passivating modified that catalyst carries out water vapour after with the binding agent moulding again.When being raw material with the mixed c 4, be reflected at 530 ℃, 0.2MPa, WHSV is 0.65h
-1When carrying out under the condition, the initial value of aromatics yield is 50wt%, and the result of successive reaction after 450 hours is 43wt%.
A kind of aromatized catalyst that CN1341699 (2002) discloses is the Zn-Ni-ZSM-5 zeolite.When mixed c 4 500 ℃ of fixed bed reactors neutral temperatures, pressure 0.5-1MPa, WHSV are 1.0-1.5h
-1When charging was reacted under the condition, liquid was received and is 60.37wt% when reacting 40 hours, and total arenes yield is 57.30wt%; When reacting 120 hours, liquid is incorporated to 47.80wt%, and total arenes yield is reduced to 45.34wt%.
As mentioned above, the preparation modification of existing aromatized catalyst is by adopting metal oxide modified or adopting the steam treatment modification or adopt the combination modification of above two kinds of methods to finish.Metal oxide modified and steam treatment modification all have the effect of eliminating strong acid center on the catalyst and improving Lewis acid centers and Bronsted acid center ratio.Wherein, realize by the surface coverage approach with the strong acid center that metal oxide modified is eliminated on the catalyst, because metal oxide itself belongs to lewis acid, therefore can improve Lewis acid centers and Bronsted acid center ratio simultaneously by metal oxide modified.Eliminate strong acid center on the catalyst mainly by the zeolitic frameworks dealuminzation is realized with the steam treatment modification, because zeolitic frameworks aluminium correspondence is the Bronsted acid center, and be stranded in the zeolite micropore from the aluminium species that zeolitic frameworks takes off, form with non-framework aluminum produces new Lewis acid centers, therefore also can improve Lewis acid centers and Bronsted acid center ratio by the steam treatment modification.
But though have good Aromatizatian catalytic performance with the aromatized catalyst of existing method preparation, the coking and deactivation speed of catalyst is fast, and one way is short service cycle, and serviceability temperature generally all must be higher than 500 ℃.
The inventor thinks by analysis, existing aromatized catalyst preparation method's problem is, its on eliminating catalyst strong acid center and improve Lewis acid centers and Bronsted acid center ratio on the catalyst in, all reduced the effective dimensions of zeolite micropore, the result has correspondingly increased the diffusional resistance in the micropore.This is because no matter the employed metal oxide of modification is to be present in the zeolite micropore with high dispersion state or with the aggregation state, all can become the barrier in the zeolite micropore.Equally, because the non-framework aluminum species that steam treatment produces and is trapped in the zeolite micropore also are the interior barriers of zeolite micropore.These microporous barrier things that produce owing to modification have increased carbon deposit presoma (the product aromatic hydrocarbon molecule just the belongs to the carbon deposit presoma) resistance to external diffusion in the zeolite micropore, have therefore increased the chance that these carbon deposit presomas deep reaction on catalyst generates carbon deposits.
Summary of the invention
The purpose of this invention is to provide a kind of aromatized catalyst preparation method that can overcome above-mentioned deficiency.
Purpose of the present invention can realize by following two aspects: on the one hand, catalyst modification carries out as follows: at first adopt the strong acid center of steam treatment elimination catalyst surface and improve Lewis acid centers and Bronsted acid center ratio, then with the catalyst (being sour reaming) behind the dilute acid soln processing water vapor passivation, thereby make and take off from zeolitic frameworks, be stranded in the dissolved removing of non-framework aluminum in the zeolite micropore, recover the smoothness of zeolite micropore.On the other hand, be catalyst Precursors with grain size less than the silica-rich zeolite of 500 nanometers, utilize the short intrinsic advantage of little crystal grain zeolite cavity, further improve the diffusivity of aromatized catalyst.
The present invention specifically can implement as follows:
At first, prepare the silica-rich zeolite parent of grain size with hydrothermal synthesis method less than 500 nanometers.Silica-rich zeolite specifically comprises ZSM-5, ZSM-11, ZSM-8.Preparing grain size with hydrothermal synthesis method illustrates in many patent documentations and open source literature less than the method for the silica-rich zeolite of 500 nanometers, such as the method disclosed in following patent documentation and the open source literature: U.S.Pat.No.3702886, U.S.Pat.No.3709979, U.S.Pat.No.3781226, U.S.Pat.No.3926782, U.S.Pat.No.4205053, U.S.Pat.No.4289607, U.S.Pat.No.5405596, U.S.Pat.No.1334243, EP173901, EP130809, Danish Patent PR 173,486, GB1334243A, Chem.Mater 5 (1993) 452, Zeolites 14 (1994) 557, Zeolites 14 (1994) 643, J.Catal.145 (1994) 243, Mater.Res.Soc.Symp.Proc.371 (1995) 21, Aangew.Chem.Int.Ed.Engl.34 (1995) 73, Chem.Mater.7 (1995) 920, Colloid Interface Sci.170 (1995) 449, Micropor.Mater.5 (1996) 381, Zeolites 18 (1997) 97, J.Phys.Chem.B101 (1997) 10094, Micropor.Mesopor.Mater.22 (1998) 9, Micropor.Mesopor.Mater.25 (1998) 434, Chem.Comm.673 (1999), Micropor.Mesopor.Mater.31 (1999) 141, Micropor.Mesopor.Mater.31 (1999) 241, Micropor.Mesopor.Mater.39 (2000) 393, Inorg.Chem.39 (2000) 2279, Micropor.Mesopor.Mater.50 (2001) 121-128, Micropor.Mesopor.Mater.43 (2001) 51-59, Mater.Sci.Eng.C 19 (2002) 111-114.Therefore, any engineer who is familiar with this area can synthesize the silica-rich zeolite of the said grain size of the present invention less than 500 nanometers according to existing method hydro-thermal.According to the common way in this area, adopt X-ray polycrystal powder diffraction approach and scanning (transmission) electron microscope method that zeolite structured and zeolite grain size are confirmed respectively.
The zeolite powder that obtains from hydro-thermal is synthetic belongs to the former powder of inactive sodium type.The former powder preparation cost of na-pretreated zeolite is invented said catalyst, should at first be made into hydrogen type catalyst according to the following steps:
At first, the former dried bean noodles of na-pretreated zeolite is dry, temperature-programmed calcination.Dry preference temperature scope is that dry atmosphere is air atmosphere, gets drying time 3～12 hours.The preference temperature scope of temperature-programmed calcination is 300～600 ℃, and calcination atmosphere is an air atmosphere, and roasting time was got 3～24 hours.The purpose of roasting is to remove the organic formwork agent that occupies in zeolite cavity.Adopt the temperature programming method can prevent that organic compound combustion is too violent, thereby avoid the inner hot-spot of zeolite crystal, destroy zeolite crystal structure.As a special case, said drying is carried out under 110 ℃, gets drying time 3 hours; Said temperature-programmed calcination carries out in Muffle furnace, and temperature-rising method is: rise to 300 ℃ from room temperature with the heating rate of 1 ℃/min, 300 ℃ of following constant temperature 1 hour; Be warming up to 400 ℃ with same heating rate again, 400 ℃ of following constant temperature 1 hour; Be warming up to 500 ℃ with same heating rate again, 500 ℃ of following constant temperature 1 hour; Be warming up to 550 ℃ with same heating rate again, 550 ℃ of following constant temperature 12 hours.
Secondly, the na-pretreated zeolite powder of taking off organic formwork agent is mixed with a certain amount of aluminium oxide, and with 10% an amount of rare nitric acid (percentage by weight) with spare, carry out compressing tablet or extrusion then according to a conventional method or shoot out or roller forming.Wherein, the butt weight ratio optimum range of little crystal grain zeolite and aluminium oxide is 1:9～9:1.If the content of zeolite is lower than this scope, then activity of such catalysts and poor stability.Otherwise if the content of zeolite is higher than this scope, then catalyst granules is easily broken.After the moulding, granular na-pretreated zeolite is carried out drying and roasting.Dry suitable condition as mentioned above.The suitable condition of roasting is: air atmosphere, 500～600 ℃, 3～8 hours.The purpose of roasting herein is the mechanical strength that strengthens particle.As a special case, said zeolite is molded on the twin-screw banded extruder and carries out, and bar footpath size is elected 1 millimeter as, and the butt weight ratio of zeolite and aluminium oxide is elected 8:2 as, and wherein aluminium oxide is provided by boehmite.Drying is carried out under 110 ℃, and be 3 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.
Again secondly,, the little crystal grain zeolite granular of moulding is exchanged with ammonium salt, make hydrogen type catalyst.The ammonium salt exchange is at room temperature carried out, the ammonium concentration optimum range of used exchange liquid is 0.1～1.0 mol, the liquid-solid volume ratio optimum range of exchange liquid and zeolite granular solid is 1～100, and the exchange number of times is 1～5 time, and be 0.5～10 hour each swap time.After each exchange is finished, outwell raffinate, add fresh exchange liquid.Ammonium ion ammonium nitrate in the exchange liquid, ammonium salts such as ammonium chloride, ammonium acetate or ammonium carbonate provide.After all ammonium exchange work is finished, outwell raffinate, spend the deionised water zeolite granular 1 time.Then, with the zeolite granular drying that exchanged, roasting.Dry suitable condition as mentioned above.The suitable condition of roasting is: air atmosphere, 500～600 ℃, 3～8 hours.The purpose of roasting herein is to discharge ammonia, and it is acid that zeolite is obtained.As a special case, the ammonium nitrate solution of 0.6M is used in said ammonium salt exchange, and the liquid-solid volume ratio of exchange liquid and zeolite granular solid elects 10 as, and the exchange number of times is 4 times, and be 1 hour each swap time.Drying is carried out under 110 ℃, and be 3 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.
On the basis of above-mentioned hydrogen type catalyst,, can obtain the said aromatized catalyst of the present invention further according to the following steps modification:
At first, above-mentioned hydrogen zeolite catalyst is carried out the water vapour Passivation Treatment: steam treatment can be carried out in well-known fixed bed reactors easily, and steam treatment can adopt pure water steam, also the steam that can adopt air or nitrogen to carry.Confirm that through research when carrying out steam treatment, the appropriate volume percentage of water vapour is 1%～100% in the atmosphere, balance gas is air or nitrogen; The preference temperature scope of steam treatment is 400～800 ℃; The suitable pressure limit of steam treatment is normal pressure～5.0MPa; The water inlet amount of amounting to by pure water steam (weight of the water that passes through on the unit fixed bed reactors cross-sectional area in the unit interval) optimum range be 0.1～1000 gram * hour
-1* square centimeter
-1The optimum range of steam treatment time is 5 minutes～200 hours under these conditions.
Secondly, handle carrying out sour reaming through the catalyst after the steam treatment modification: sour reaming is handled and can be carried out in acidproof container easily.Confirm that through research sour reaming is handled can select any aqueous acid in hydrochloric acid, nitric acid or the sulfuric acid, perhaps selects the mixed acid solution of above inorganic acid; Can also select any aqueous acid in formic acid, acetate or the citric acid, perhaps select above organic acid mixed acid solution; State in the choice under the situation of inorganic acid, the hydrogen proton concentration optimum range in the acid solution is 0.001 mol～5.0 mol; State in the choice under the organic acid situation, the concentration expressed in percentage by weight optimum range of solute is 0.1%～20% in the acid solution; The acid reaming is handled and is carried out under normal pressure, and suitable temperature range is 1 ℃～80 ℃.The acid reaming is handled and can be carried out under static situation, also can circulate under the situation at acid solution and carry out.Under these conditions, the suitable time scope of sour reaming is 0.5～200 hour.After the acid reaming finishes, with deionized water with catalyst wash to neutral, be dried then, roasting, make finished catalyst.Drying is carried out under 110 ℃, and be 3 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.
Effect of the present invention can be in order to down method evaluation:
Evaluate catalysts acidity adopts pyridine adsorption-infra-red sepectrometry.Pyridine adsorption-infra-red sepectrometry is the conventional method that this area is used to distinguish Bronsted acid center and Lewis acid centers.This method can provide the catalyst acid strength information simultaneously.Any engineer who is familiar with this area can measure catalyst acidity of the present invention according to the experimental procedure of pyridine adsorption-infra-red sepectrometry of putting down in writing in the document.
Evaluate catalysts micropore diffusion smoothness adopts n-hexane and cyclohexane adsorbance method.The adsorbance of measuring hydrocarbon molecule probes such as n-hexane and cyclohexane is the conventional method that this area is used for characterize molecular sieve pore passage effective dimensions.The smoothness of the micropore of zeolite catalyst can characterize with the duct effective dimensions.When zeolite catalyst barrier occurs in the micropore in modifying process, the effective dimensions in its duct will reduce, and the barrier that occurs in the micropore is many more, and then the degree that reduces of zeolite cavity effective dimensions is big more.Otherwise after the barrier in the zeolite micropore is eliminated, the effective dimensions of zeolite cavity will be restored.Under identical adsorption conditions, for same hydrocarbon molecule probe, the adsorbance of measuring in same adsorption time is big more, illustrate that the adsorption rate of hydrocarbon molecule probe in zeolite micropore is fast more, that is to say, the micropore effective dimensions of determined zeolite sample is big more, and barrier is few more in the duct; Otherwise the adsorbance of measuring in same adsorption time is more little, illustrates that then the adsorption rate of hydrocarbon molecule probe in zeolite micropore is slow more, that is to say that the micropore effective dimensions of determined zeolite sample is more little, and barrier is many more in the duct.Any engineer who is familiar with this area can characterize according to the experimental procedure of n-hexane of putting down in writing in the document and the cyclohexane adsorbance method micropore diffusion smoothness to catalyst of the present invention.
Aromatization activity and the anti-coking deactivation stability thereof of estimating catalyst of the present invention adopt conventional fixed bed compressive reaction method.The raw material of fixed bed reaction is a carbon 4 liquid gas, does not use any carrier gas in the course of reaction.As a special case, the raw material of fixed bed reaction is the carbon 4 liquid gas of catalytic cracking unit by-product, and wherein the content of various C 4 olefins is no less than 50%.The suitable condition scope of reaction is: 300～500 ℃ of reaction temperatures, the reaction pressure scope is 0.1～5MPa, charging air speed (WHSV) 0.05～20h of carbon 4 liquid gas
-1Reaction temperature is too low or the charging air speed is too big, all is unfavorable for the alkene aromatization.Otherwise reaction temperature is too high or the charging air speed is too little, and then catalyst coking inactivation is serious.
The benefit of effect of the present invention is: to the modification that is intended to regulate its acid strength and lewis acid and Bronsted acid ratio that catalyst carries out, can keep the diffusion smoothness of catalyst mesolite micropore; By select grain size less than the silica-rich zeolite of 500 nanometers as catalyst Precursors, make the zeolite micropore in the catalyst more help molecular diffusion.Therefore, low with the aromatized catalyst reaction temperature of the present invention's preparation, the aromatization activity height, and anti-coking deactivation ability is strong.In addition,, do not use metal, particularly do not use the metal of resource shortage such as gallium etc., so the catalyst cost of the present invention's preparation is low because the present invention is few to the modification procedure of catalyst.
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Preparation of Catalyst embodiment 1: with grain size is that the sodium type ZSM-5 zeolite of 20-50 nanometer prepares hydrogen zeolite catalyst.
(1) taking off the agent of organic amine template handles: getting grain size is the sodium type ZSM-5 zeolite powder (SiO of 20-50 nanometer
2/ Al
2O
3Mol ratio 26), 110 ℃ dry 3 hours down, in Muffle furnace, carry out temperature-programmed calcination then, temperature-rising method is: rise to 300 ℃ from room temperature with the heating rate of 1 ℃/min, 300 ℃ of following constant temperature 1 hour; Be warming up to 400 ℃ with same heating rate again, 400 ℃ of following constant temperature 1 hour; Be warming up to 500 ℃ with same heating rate again, 500 ℃ of following constant temperature 1 hour; Be warming up to 550 ℃ with same heating rate again, 550 ℃ of following constant temperature 12 hours.
(2) moulding: according to the butt weight ratio 8:2 of zeolite and aluminium oxide, get na-pretreated zeolite 80 grams (butt) that burnt the agent of organic amine template respectively, boehmite 20 grams (butt), after hand mix is even, making binding agent with rare nitric acid of 10% mixes and pinches, carry out extruded moulding with a twin-screw banded extruder then, bar footpath size is elected 1 millimeter as.Zeolite granular behind the extruded moulding 110 ℃ dry 3 hours down, in Muffle furnace, carry out roasting at last, temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.
(3) ammonium exchange preparation hydrogen type catalyst: ammonium exchanges the ammonium nitrate solution with 0.6 mol, and the liquid-solid volume ratio of exchange liquid and zeolite granular solid is 10, exchanges 4 times, and be 1 hour each swap time, and liquid is changed in the centre.Zeolite granular after exchange is finished carries out drying and handles through the deionized water washing under 110 ℃, be 3 hours drying time.Then, carry out roasting deamination gas in Muffle furnace, temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.So far, obtain hydrogen type catalyst HZSM-5 (A).
Preparation of Catalyst embodiment 2: be the hydrogen zeolite catalyst of the low molecular sieve content of sodium type ZSM-5 zeolite preparation of 20-50 nanometer with grain size.
Repeat embodiment 1, but used 20-50 nano-ZSM-5 zeolite (SiO
2/ Al
2O
3Mol ratio 26) with the butt weight ratio 50:50 of aluminium oxide.Correspondingly, resulting hydrogen type catalyst is decided to be HZSM-5 (B).
Preparation of Catalyst embodiment 3: with grain size is that the sodium type ZSM-5 zeolite of 300-500 nanometer prepares hydrogen zeolite catalyst.
Repeat embodiment 1, but used sodium type ZSM-5 zeolite powder grain size is 300-500 nanometer (SiO
2/ Al
2O
3Mol ratio 26).Correspondingly, resulting hydrogen type catalyst is decided to be HZSM-5 (C).
Preparation of Catalyst embodiment 4: with grain size is that the sodium type ZSM-11 zeolite of 100-500 nanometer prepares hydrogen zeolite catalyst.
Repeat embodiment 1, but the former powder of used na-pretreated zeolite is the ZSM-11 (SiO of grain size in the 100-500 nanometer range
2/ Al
2O
3Mol ratio 26).Correspondingly, resulting hydrogen type catalyst is decided to be HZSM-11.
Preparation of Catalyst embodiment 5: with grain size is that the sodium type ZSM-8 zeolite of 90-300 nanometer prepares hydrogen zeolite catalyst.
Repeat embodiment 1, but the former powder of used na-pretreated zeolite is the ZSM-8 (SiO of grain size in the 90-300 nanometer range
2/ Al
2O
3Mol ratio 20).Correspondingly, resulting hydrogen type catalyst is decided to be HZSM-8.
Preparation of Catalyst embodiment 6: prepare modified catalyst of the present invention from hydrogen zeolite catalyst
Get each 3 gram of Preparation of Catalyst embodiment 1～example 5 prepared hydrogen zeolite catalyst HZSM-5 (A), HZSM-5 (B), HZSM-5 (C), HZSM-11 and HZSM-8 and be processed into the cylindricality particle of φ 1 * (2-3), successively it is loaded on the flat-temperature zone of the fixed bed reactors of internal diameter φ 7 then, carries out steam treatment.Steam treatment is carried out in 100% water vapour atmosphere, the temperature of steam treatment is 550 ℃, the pressure of steam treatment is normal pressure, the water inlet amount of reactor (weight of the water that passes through on the unit fixed bed reactors cross-sectional area in the unit interval) be 7.8 grams * hour
-1* square centimeter
-1, the steam treatment time is 3 hours.Prepare the HNO of 0.6 mol
3The aqueous solution (that is, the hydrogen proton concentration in the acid solution is 0.6 mol) carries out sour reaming to above-mentioned steam treatment catalyst to be handled.The condition that the acid reaming is handled is: HNO
3The liquid-solid mass ratio of solution and catalyst is got 5:1, and sour reaming is handled under the condition of normal pressure and 25 ℃ and carried out with static immersion way, and soak time is 24 hours.After the acid reaming finishes, with deionized water with catalyst wash to neutral, be dried then, roasting, make finished catalyst.Drying is carried out under 110 ℃, and be 3 hours drying time; Roasting is carried out in Muffle furnace, and temperature-rising method is: directly rise to 550 ℃ from room temperature with the heating rate of 3 ℃/min, constant temperature is 3 hours then.Remember successively through the catalyst of above-mentioned steps modification and to be SIHZSM-5 (A), SIHZSM-5 (B), SIHZSM-5 (C), SIHZSM-11 and SIHZSM-8.
Preparation of Catalyst embodiment 7: adopt different steam treatment temperature to prepare modified catalyst of the present invention from hydrogen zeolite catalyst
Get the prepared hydrogen zeolite catalyst HZSM-5 (A) of Preparation of Catalyst embodiment 1, repeat embodiment 6, but the steam treatment temperature is respectively 450 ℃ and 700 ℃, correspondingly, the steam treatment time was respectively 100 hours and 0.5 hour, and then resulting modified catalyst is followed successively by SIHZSM-5 (A)-01 and SIHZSM-5 (A)-02.
Preparation of Catalyst embodiment 8: adopt different steam treatment atmosphere to prepare modified catalyst of the present invention from hydrogen zeolite catalyst
Get the prepared hydrogen zeolite catalyst HZSM-5 (A) of Preparation of Catalyst embodiment 1, repeat embodiment 6, but difference bubbling air in the steam treatment process (through dedusting, carbon dioxide removal and dry the processing) and nitrogen (common steel cylinder nitrogen, purity is greater than 99%), in perfect gas, water vapour shared percentage by volume in gaseous mixture is 15%, correspondingly, the water inlet amount of amounting to (weight of the water that passes through on the unit fixed bed reactors cross-sectional area in the unit interval) by pure water steam get 1.0 grams * hour
-1* square centimeter
-1, the pressure of steam treatment adopts 2.0MPa, and the steam treatment time got 48 hours, and then resulting modified catalyst is followed successively by SIHZSM-5 (A)-03 and SIHZSM-5 (A)-04.
Preparation of Catalyst embodiment 9: with different inorganic acid solutions the steam treatment catalyst is carried out reaming Processing of Preparation modified catalyst of the present invention
Get the prepared hydrogen zeolite catalyst HZSM-5 (A) of Preparation of Catalyst embodiment 1, repeat embodiment 6, but the acid solution that uses in sour reaming step is respectively 0.01 mol nitric acid, 2 mol nitric acid, 0.6 mol hydrochloric acid, 0.6 mol sulfuric acid, 0.2 the nitration mixture of mol nitric acid and 0.2 mol sulfuric acid, then resulting modified catalyst is followed successively by SIHZSM-5 (A)-05, SIHZSM-5 (A)-06, SIHZSM-5 (A)-07, SIHZSM-5 (A)-08, SIHZSM-5 (A)-09.
Preparation of Catalyst embodiment 10: with different organic acids solution the steam treatment catalyst is carried out reaming Processing of Preparation modified catalyst of the present invention
Get the prepared hydrogen zeolite catalyst HZSM-5 (A) of Preparation of Catalyst embodiment 1, repeat embodiment 6, but the acid solution that uses is respectively 0.5% citric acid, 5% citric acid in sour reaming step, 15% citric acid, 5% formic acid, 5% acetate, the mixed acid that 2.5% formic acid and 2.5% acetate are formed, the acid reaming is handled and is carried out under normal pressure, but temperature is 80 ℃, and acid solution circulates, and the time of sour reaming got 120 hours.Then resulting modified catalyst is followed successively by SIHZSM-5 (A)-10, SIHZSM-5 (A)-11, SIHZSM-5 (A)-12, SIHZSM-5 (A)-13, SIHZSM-5 (A)-14, SIHZSM-5 (A)-15.
Preparation of Catalyst embodiment 11 (comparative example): with grain size is a sodium type ZSM-5 zeolite preparation modified catalyst through steam treatment of 20-50 nanometer
Get the prepared hydrogen zeolite catalyst HZSM-5 (A) of Preparation of Catalyst embodiment 1, repeat embodiment 6, but catalyst only carries out steam treatment, do not carry out sour reaming and handle, prepared modified catalyst note is SHZSM-5 (A).
Preparation of Catalyst embodiment 12 (comparative example): with grain size is that the big crystal grain sodium type ZSM-5 zeolite of 1000-2000 nanometer prepares modified catalyst
Getting grain size is the big crystal grain sodium type ZSM-5 zeolite (SiO of 1000-2000 nanometer
2/ Al
2O
3Mol ratio 26), repeat Preparation of Catalyst embodiment 1 and Preparation of Catalyst embodiment 6, prepared modified catalyst note is SIHZSM-5 (LR).
Catalyst characterization embodiment 1: with the acidity of pyridine adsorption infrared spectroscopic determination catalyst
Carry out pyridine adsorption-infrared spectrum according to conventional way and take the photograph the spectrum experiment.Wherein, the sample purification temperature is 500 ℃, and vacuum is 0.07 handkerchief, and the clarification time is 1 hour, and the pyridine adsorption temperature is a room temperature.The saturated back of pyridine adsorption sample outgases under 150 ℃ and 350 ℃ of temperature respectively and at 1000 centimetres
-1～2000 centimetres
-1Picked-up infrared absorption spectroscopy in the wave-number range.According to generally accepted knowledge, with sample at 1540 centimetres
-1The absworption peak ownership at place is the Bronsted acid center, and sample is at 1450 centimetres
-1The absworption peak ownership at place is Lewis acid centers.The present invention represents that with the Bronsted acid center and the relative peak height of the pairing absworption peak of Lewis acid centers the quantity of Bronsted acid center and Lewis acid centers (is expressed as the quantity in acid site on the Unit Weight catalyst, unit: mM/gram), weigh the regulating effect of modification with lewis acid (L acid) center and the quantity at Bronsted acid (B acid) center of sample under 150 ℃ than (that is: total L acid/total B acid), with the Lewis acid centers of sample 350 ℃ under and the quantity sum at Bronsted acid center (strong L acid+strong B acid) measurement modification elimination effect for the catalyst strong acid center for catalyst Lewis acid centers and Bronsted acid center.Its result is as follows:
The total L acid/strong L acid of total B acid+strong B acid
HZSM-5(A)： 1.39 0.36
HZSM-5(B)： 1.42 0.21
HZSM-5(C)： 1.25 0.43
HZSM-11： 1.30 0.31
HZSM-8： 1.20 0.25
SIHZSM-5(A)： 2.43 0.20
SIHZSM-5(B)： 2.50 0.11
SIHZSM-5(C)： 2.20 0.23
SIHZSM-11： 2.50 0.18
SIHZSM-8： 2.29 0.12
SIHZSM-5(A)-01： 1.78 0.29
SIHZSM-5(A)-02： 3.56 0.08
SIHZSM-5(A)-03： 2.15 0.26
SIHZSM-5(A)-04： 2.11 0.25
SIHZSM-5(A)-05： 2.35 0.19
SIHZSM-5(A)-06： 2.50 0.20
SIHZSM-5(A)-07： 2.44 0.21
SIHZSM-5(A)-08： 2.39 0.19
SIHZSM-5(A)-09： 2.40 0.22
SIHZSM-5(A)-10： 2.08 0.18
SIHZSM-5(A)-11： 2.20 0.19
SIHZSM-5(A)-12： 2.50 0.15
SIHZSM-5(A)-13： 2.40 0.22
SIHZSM-5(A)-14： 2.42 0.20
SIHZSM-5(A)-15： 2.40 0.20
SHZSM-5(A) 2.00 0.18
SIHZSM-5(LR) 2.51 0.26
Catalyst characterization embodiment 2: with the micropore diffusion smoothness of n-hexane and cyclohexane adsorbance evaluate catalysts
Carry out n-hexane and cyclohexane adsorbance determination experiment according to conventional way.Wherein, sample purifies 30 minutes in flowing nitrogen atmosphere, and purification temperature is 350 ℃, and adsorption temp is 25 ℃, and the adsorbate dividing potential drop is 20 millimetress of mercury, and atmospheric pressure is 760 millimetress of mercury, and adsorption time is 5 hours.The present invention with the adsorbance of n-hexane and cyclohexane than the restricted index that is defined as catalyst mesolite micropore.The present invention reflects the resistance situation of zeolite micropore to the diffusion molecule with the restricted index of zeolite micropore: restricted index is big more, represents that then zeolite micropore is big more for the resistance of diffusion molecule.Its result is as follows:
The duct restricted index
HZSM-5(A)： 1.12
HZSM-5(B)： 1.10
HZSM-5(C)： 1.16
HZSM-11： 1.13
HZSM-8： 1.11
SIHZSM-5(A)： 1.14
SIHZSM-5(B)： 1.13
SIHZSM-5(C)： 1.16
SIHZSM-11： 1.14
SIHZSM-8： 1.15
SIHZSM-5(A)-01： 1.13
SIHZSM-5(A)-02： 1.15
SIHZSM-5(A)-03： 1.12
SIHZSM-5(A)-04： 1.13
SIHZSM-5(A)-05： 1.15
SIHZSM-5(A)-06： 1.11
SIHZSM-5(A)-07： 1.13
SIHZSM-5(A)-08： 1.13
SIHZSM-5(A)-09： 1.14
SIHZSM-5(A)-10： 1.16
SIHZSM-5(A)-11： 1.14
SIHZSM-5(A)-12： 1.10
SIHZSM-5(A)-13： 1.14
SIHZSM-5(A)-14： 1.14
SIHZSM-5(A)-15： 1.13
SHZSM-5(A) 1.25
SIHZSM-5(LR) 1.50
Aromatization embodiment 1
Carry out the aromatization experiment in the fixed bed pressurized reactor of routine, reaction raw materials is the carbon 4 liquid gas of catalytic cracking unit by-product, specifically consists of: iso-butane (i carbon four
0): 26.24%, normal butane (n carbon four
0): 11.53%, positive isobutene (n, i carbon four
=): 29.54%, anti-butylene (t carbon four
=): 18.60%, maleic (c carbon four
=): 13.86%, carbon five (C
5): 0.23%, do not use any carrier gas in the course of reaction, catalyst is SIHZSM-5 (A), and loadings is 2 grams, and reaction temperature is 400 ℃, and reaction pressure is 3MPa (using the nitrogen pressurising before the reaction beginning), the charging air speed (WHSV) of carbon 4 liquid gas is 0.8h
-1, sample analysis in tandem reaction sequence, its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), olefin(e) centent (W, weight %) was respectively in reaction in the 1st day, the 6th day and the 10th day in arene content in the gasoline (Z, weight %) and the gasoline:
SIHZSM-5 (A) X, % Y, weight % Z, weight % W, weight %
The 1st day 98 70 53 1.8
The 6th day 98 73 49 2.1
The 10th day 97 74 46 2.5
Aromatization embodiment 2
Repeat aromatization embodiment 1, but reaction temperature is respectively 370 ℃ and 450 ℃, its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), olefin(e) centent (W, weight %) in reaction the 6th day was in arene content in the gasoline (Z, weight %) and the gasoline:
SIHZSM-5 (A) X, % Y, weight % Z, weight % W, weight %
370℃ 88 54 35 18.2
450℃ 99.5 77 64 1.5
Aromatization embodiment 3
Repeat aromatization embodiment 1, but reaction pressure is respectively 0.1MPa, 1.0MPa and 4MPa, its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), olefin(e) centent (W, weight %) in reaction the 6th day was in arene content in the gasoline (Z, weight %) and the gasoline:
SIHZSM-5 (A) X, % Y, weight % Z, weight % W, weight %
0.1MPa 90 66 34 20
1.0Mpa 94 68 40 15
4.0Mpa 99 75 51 2.0
Aromatization embodiment 4
Repeat aromatization embodiment 1, but the charging air speed (WHSV) of carbon 4 liquid gas is respectively 0.1
-1And 5h
-1, its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), and olefin(e) centent (W, weight %) in reaction the 6th day was in arene content in the gasoline (Z, weight %) and the gasoline:
SIHZSM-5 (A) X, % Y, weight % Z, weight % W, weight %
WHSV＝0.1h
-1 99 67 58 1.0
WHSV＝5h
-1 75 48 29 26
Aromatization embodiment 5
Repeat aromatization embodiment 1, but catalyst system therefor is followed successively by SIHZSM-5 (B), SIHZSM-5 (C), SIHZSM-11, SIHZSM-8, SIHZSM-5 (A)-01, SIHZSM-5 (A)-02, SIHZSM-5 (A)-03, SIHZSM-5 (A)-04, SIHZSM-5 (A)-05, SIHZSM-5 (A)-06, SIHZSM-5 (A)-07, SIHZSM-5 (A)-08, SIHZSM-5 (A)-09, SIHZSM-5 (A)-10, SIHZSM-5 (A)-11, SIHZSM-5 (A)-12, SIHZSM-5 (A)-13, SIHZSM-5 (A)-14, SIHZSM-5 (A)-15, its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), arene content (Z in the gasoline, weight %) olefin(e) centent (W, weight %) was respectively in reaction on the 6th day and in the gasoline:
X, % Y, weight % Z, weight % W, weight %
SIHZSM-5(B)： 91 64 39 10.6
SIHZSM-5(C)： 96 68 43 7.5
SIHZSM-11： 97 69 46 4.3
SIHZSM-8： 96 67 44 4.9
SIHZSM-5(A)-01： 86 53 34 18
SIHZSM-5(A)-02： 97 70 47 3.1
SIHZSM-5(A)-03： 93 65 43 5.2
SIHZSM-5(A)-04： 92 67 40 7.9
SIHZSM-5(A)-05： 95 64 41 8.3
SIHZSM-5(A)-06： 97 70 48 1.9
SIHZSM-5(A)-07： 97 69 47 2.2
SIHZSM-5(A)-08： 96 71 47 2.0
SIHZSM-5(A)-09： 95 63 42 4.7
SIHZSM-5(A)-10： 90 59 37 12.5
SIHZSM-5(A)-11： 93 61 40 8.0
SIHZSM-5(A)-12： 97 70 46 3.3
SIHZSM-5(A)-13： 94 62 42 7.0
SIHZSM-5(A)-14： 94 60 39 9.2
SIHZSM-5(A)-15： 93 58 37 11.4
Aromatization embodiment 6 (comparative example)
Repeat aromatization embodiment 1, but catalyst system therefor is followed successively by SHZSM-5 (A), SIHZSM-5 (LR), its C 4 olefin conversion ratio (X, %), carbon five above liquid are received (Y, weight %), arene content (Z in the gasoline, weight %) olefin(e) centent (W, weight %) was respectively in reaction on the 6th day and in the gasoline:
X, % Y, weight % Z, weight % W, weight %
SHZSM-5(A)： 86 48 31 24
SIHZSM-5(LR)： 80 42 24 29
Claims (4)
1. carbon four liquefied petroleum gas carry out the Preparation of catalysts method of aromatisation in fixed bed reactors, it is characterized in that, the parent of catalyst is the silica-rich zeolite of grain size less than 500 nanometers, after the butt weight ratio moulding of zeolite parent and aluminium oxide with 1:9～9:1, with concentration is the ammonium ion solution of 0.1～1.0 mol, liquid-solid volume ratio according to 1～100 is exchanged into hydrogen type catalyst, then under 400～800 ℃ of temperature, with the above-mentioned hydrogen type catalyst of steam treatment 5 minutes～200 hours, then under 1 ℃～80 ℃, the sour reaming that above-mentioned steam treatment catalyst carried out 0.5～200 hour is handled with acid solution, the gained catalyst can be 300 ℃～500 ℃ in reaction temperature, reaction pressure is 0.1MPa～5MPa, and the charging air speed of carbon four liquefied petroleum gas is 0.05h
-1～20h
-1Do not use under the condition of any carrier gas, in fixed bed reactors, make carbon four liquefied petroleum gas aromatisation.
2. preparation method according to claim 1 is characterized in that, the parent of catalyst is meant the ZSM-5 zeolite of grain size less than 500 nanometers, ZSM-8 zeolite or ZSM-11 zeolite.
3. preparation method according to claim 1, it is characterized in that the acid solution that is used for sour reaming processing is meant hydrochloric acid solution, salpeter solution, the mixed acid solution of sulfuric acid solution or above inorganic acid requires the hydrogen proton concentration in the acid solution to satisfy 0.001 mol～5.0 mol.
4. preparation method according to claim 1, it is characterized in that the acid solution that is used for sour reaming processing is meant formic acid solution, acetic acid solution, citric acid solution or above organic acid mixed acid solution require the concentration expressed in percentage by weight of solute in the acid solution to satisfy 0.1%～20%.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857808B (en) * | 2010-06-17 | 2014-02-26 | 宁夏宝塔石化集团有限公司 | Method for preparing gasoline from liquefied gas through aromatization and fixed bed reactor |
| CN102649677B (en) * | 2011-02-25 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon by aromatizing C4 hydrocarbon |
| CN102343279A (en) * | 2011-07-18 | 2012-02-08 | 天津市福生染料厂 | Method for preparing catalyst used in preparation of clean gasoline from C4 olefin |
| CN102899084B (en) * | 2011-07-25 | 2014-10-15 | 中国石油天然气股份有限公司 | Method for co-production of pyrolysis raw material for ethylene through C4 hydrocarbon aromatization |
| CN102895990A (en) * | 2011-07-29 | 2013-01-30 | 中国石油天然气股份有限公司 | Light hydrocarbon aromatization catalyst and preparation method thereof |
| CN102389830A (en) * | 2011-10-31 | 2012-03-28 | 中国科学院大连化学物理研究所 | Preparation method of superfine cocrystallized molecular sieve catalyst |
| CN103657707B (en) * | 2012-09-05 | 2016-04-13 | 中国石油化工股份有限公司 | Preparation method of low carbon hydrocarbon aromatization catalyst |
| CN103831127A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Catalyst for C4 hydrogenation aromatization and preparation method |
| CN103831128B (en) * | 2012-11-27 | 2016-12-21 | 中国石油天然气股份有限公司 | A kind of modified nano molecular sieve hydroaromatization catalyst and preparation method |
| CN103834435B (en) * | 2012-11-27 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of two-stage reaction technique of carbon 4 liquid gas hydroaromatization |
| CN103831126A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | C4 liquefied gas hydrogenation aromatization catalyst and preparation method thereof |
| CN104923283B (en) * | 2015-05-27 | 2017-10-31 | 安徽皖东树脂科技有限公司 | A kind of liquefied petroleum catalyst of carbon four and preparation method thereof |
| CN107282088A (en) * | 2016-04-01 | 2017-10-24 | 神华集团有限责任公司 | The method of organic oxygen-containing compound olefin hydrocarbon molecules sieve catalyst and preparation method thereof and organic oxygen-containing compound alkene |
| CN107930676B (en) * | 2016-10-12 | 2021-05-14 | 中国科学院大连化学物理研究所 | ZSM-11 catalyst for olefin aromatization and preparation method thereof |
| US11097263B2 (en) * | 2019-08-30 | 2021-08-24 | China University of Petroleum—Beijing | Aromatization catalyst, preparation method, regeneration method thereof, and aromatization method |
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