CN1762593A - Method for preparing toluene disproportionation zeolitic catalyst with increased para-selectivity - Google Patents
Method for preparing toluene disproportionation zeolitic catalyst with increased para-selectivity Download PDFInfo
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- CN1762593A CN1762593A CNA2005100945897A CN200510094589A CN1762593A CN 1762593 A CN1762593 A CN 1762593A CN A2005100945897 A CNA2005100945897 A CN A2005100945897A CN 200510094589 A CN200510094589 A CN 200510094589A CN 1762593 A CN1762593 A CN 1762593A
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- catalyst
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- zeolite
- acid
- toluene
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000003054 catalyst Substances 0.000 title claims abstract description 187
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 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 53
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 23
- 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
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 19
- 239000002689 soil Substances 0.000 claims description 19
- 241001494479 Pecora Species 0.000 claims description 16
- 235000009508 confectionery Nutrition 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 235000015165 citric acid Nutrition 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229960005137 succinic acid Drugs 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 43
- 238000012986 modification Methods 0.000 abstract description 43
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 28
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 8
- 239000008096 xylene Substances 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000004927 clay Substances 0.000 abstract 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 82
- 230000000694 effects Effects 0.000 description 32
- 230000008569 process Effects 0.000 description 24
- 238000012545 processing Methods 0.000 description 24
- 229910052710 silicon Inorganic materials 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- -1 drippolene Substances 0.000 description 22
- 239000010703 silicon Substances 0.000 description 22
- 238000000151 deposition Methods 0.000 description 20
- 229920001296 polysiloxane Polymers 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 9
- 238000010306 acid treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003607 modifier Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 150000003961 organosilicon compounds Chemical group 0.000 description 4
- 208000035126 Facies Diseases 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001723 mesolite Inorganic materials 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 238000005554 pickling Methods 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
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- 238000006424 Flood reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method for zeolite catalyst to enhance para-position selectivity for toluene disproportionation, which comprises: adding natural clay adhesive and assist-extrusion agent contained alumina and silicon dioxide into hydrogen-type zeolite powder to form, treating with organic acid; using ethyl silicate for chemical liquid-phase deposition modification to dried sample; baking, aging, baking, and treating with 100% water vapor. This product can improve selectivity obviously, can achieve 96.5wt% to xylene selectivity when the toluene conversion is 23wt%, and needs low cost.
Description
Technical field:
The present invention relates to a kind of method for preparing catalyst, relate in particular to a kind of zeolite catalyst preparation method who increases the para-selectivity methylbenzene shape selective disproportionation.
Background technology:
Paraxylene (PX) is a primary raw material of producing p-phthalic acid (PTA) in the polyester industrial, industrial utilization reformation gasoline, drippolene, toluene, C
9Aromatic hydrocarbons and mixed xylenes are raw material, use modenite, the Y zeolite catalyst as active component usually, make C by disproportionation, transalkylation and isomerization
8Aromatic hydrocarbons, but can only obtain the dimethylbenzene (contraposition a: position: ortho position=24%: 53%: 23%) that thermodynamical equilibrium is formed., must make paraxylene through adsorbing separation or Crystallization Separation, and this separation process complexity, energy consumption is big.
People such as Chang are in J.Amer.Chem.Soc.101 (6783), point out in 1979 with in micro-pore zeolite such as ZSM-5 zeolite carry out the alternative paraxylene that generates of methylbenzene shape selective disproportionation.The ZSM-5 zeolite constitutes pore canal system by 10 yuan of oxygen rings, has medium sized aperture and aperture.The aperture characteristics permission molecular dynamics diameter of ZSM-5 zeolite is that the paraxylene of 6.3 spreads rapidly, can seriously hinder ortho-xylene and meta-xylene diffusion that molecular diameter is 6.9 simultaneously.In the toluene disproportionation process system, there is following relation in the diffusion coefficient of each species in the ZSM-5 duct: benzene 〉=toluene＞ethylbenzene ≈ paraxylene＞ortho-xylene ≈ meta-xylene, this means toluene disproportionation process is carried out the possibility that the product shape is selected, can obtain to be higher than in the dimethylbenzene product paraxylene content of isomer of thermodynamical equilibrium concentration far away.Though the duct of ZSM-5 zeolite makes paraxylene that the diffusion advantage be arranged, but because there is the non-shape acid position of selecting in outer surface of zeolite, the rich contraposition product that generates in zeolite cavity can obtain being tending towards the final mixed xylenes product that thermodynamical equilibrium distributes in the rapid secondary isomerization of outer surface.In order to obtain higher para-selectivity, must carry out modification to the ZSM-5 catalyst.
There are several method of modifying to improve the para-selectivity of ZSM-5 catalyst technically.Wherein Lee's book line etc. is at the chemistry of fuel journal, and 13 (211) 1985, people such as Chang discloses a kind of with phosphorus, magnesium and rare earth modified ZSM-5 prepare zeolite method and the application in toluene disproportionation in CN 85102764 at J.Amer.Chem.Soc.101 (6783) and Chen Lianzhang.The ZSM-5 zeolite catalyst through phosphorus, magnesium-modified after, also available halide, carbon dioxide, nitrogen-containing compound, sulfur-containing compound are further handled catalyst to improve para-selectivity.But these processing methods can obviously reduce activity of such catalysts, even react under very high temperature, conversion ratio is still not high, and P elements easy loss under reaction condition also is a defective of this technology.
In the organic compound atmosphere at high temperature, zeolite can be modified the aperture by pre-coking process, covers outer surface Bronsted acid center to improve the paraxylene selectivity of toluene disproportionation process.People such as Low are at USP.5, and 321,184 (1994) disclose the paraxylene selectivity that improves xylene isomerization process with zeolite preprocessing process under the harsh conditions in aroamtic hydrocarbon raw material atmosphere.Because pre-coking process needs to carry out down in position, its process will be carried out step by step, and coking time is longer, causes complex technical process, and coking amount is wayward.
Modified with organosilicon compounds is to improve the very effective approach of zeolite toluene disproportionation para-selectivity, and this method is by catalyst deactivation outer surface acid position and dwindle port size, helps the formation of PX.Rudolph etc. are at USP.5, have openly reported the zeolite that several modifications are handled in 552,357 (1996), and these zeolites comprise ZSM-5, ZSM-12 and ZSM-35, and its restricted index is 1-12, m (SiO
2): m (Al
2O
3) be 10-20.These zeolites are carried out soluble amido siloxanes polymer surface dystopy (ex situ) chemical liquid deposition modify, with protection zeolite surface active sites.Simultaneously, under the disproportionated reaction condition, in toluene feed, add mass fraction and be 1% the efficient PX selective active of (gathering) siloxanes agent and carry out original position (in situ) siliceous deposits.After above-mentioned two kinds of different organosilicons processing, in the disproportionated reaction, toluene conversion is minimum to be 15%, the PX mass fraction is 90% in the product dimethylbenzene, and this method must be carried out in-situ treatment, and its process is that the modifier consumption is big, deposition is wayward, shortcomings such as complicated operating process.
The method that a kind of methylbenzene shape selective disproportionation generates paraxylene is disclosed among the CN 1100402A, this method is to contact with zeolite catalyst at the toluene that reaction will contain the agent of paraxylene selectionization the initial phase, catalyst is carried out original position adjustment selectionization, the agent of paraxylene selectionization is organo-silicon compound, mainly is selected from the comparatively complicated material of structures such as the mixture of polyphenyl methyl siloxane and dimethyl silicone polymer or methyl hydrogen cyclosiloxane, hexamethyl hydrogen cyclosiloxane, diphenyl silane.This on-the-spot selectionization of adjusting need continue 50-300 hour, and the time of selectionization phase is longer.For industrial bigger device, adjust the selectionization effect and be difficult to accurate prediction, operate wayward.
A kind of method that silica and alumina molar ratio are carried out modification less than the shape selective of 500 aluminosilicate zeolite catalyst is disclosed among the CN1124950A.This method is that catalyst is carried out at least twice dystopy selectionization processing, and wherein the step of dystopy selectionization processing is earlier catalyst to be contacted with the selection agent that is dissolved in organic facies or aqueous phase each time, then catalyst is carried out roasting.Selection agent wherein mainly is selected from siloxane polymer or amino containing silane, as 3,5-dimethylphenyl methyl polysiloxane (Dow-550) or n-pro-pyl amine silane polymer (Hydrosil2627).If the selectionization agent is selected from siloxane polymer, need it is dissolved in the organic facies, this organic facies is a kind of alkane that contains 7 carbon atoms, as dodecane.If the selectionization agent is an amino containing silane, then it is diluted to the aqueous solution, with this solution impregnation zeolite catalyst it is carried out the shape modification again.The processing of this dystopy selectionization wants just can make more than the triplicate catalyst to have good catalytic performance, uses the 3,5-dimethylphenyl methyl polysiloxane to Hydrogen ZSM-5/SiO in this patent working example 4
2Carry out 4 dystopys continuously and handle, then at 484 ℃, 3550KPa, hydrogen-hydrocarbon ratio are 2, and the little hourly space velocity of toluene feed weight is 4h
-1Carry out toluene disproportionation process under the condition, when its result was 25% when toluene conversion, the para-selectivity of catalyst was 86%.This patent also will be carried out the catalyst of dystopy selectionization processing through said method, carry out the processing of in-situ conditioning selectionization before carrying out toluene disproportionation process again, with further raising contraposition shape selectivity.USP5610112 has proposed a kind of zeolite catalyst that will contain binding agent or binder free and has handled with silicon-containing compound, and this processing is called preselectedization, the silicon compound of preselectedization use is selected from silane, siloxanes and organic amino group silane polymer, afterwards the catalyst of preselectedization modification is carried out roasting being no more than under 600 ℃ the temperature, then at 200～400 ℃, with 5～100%, the steam treatment of 50-100% preferably.Do not carry out steam treatment or only carry out simple steam treatment if only carry out preselected processing, selection of catalysts just can not improve, or even harmful.This patent is further to improve the selectivity of paraxylene, and also the catalyst to modification carries out original position adjustment selectionization before disproportionated reaction, and adjusting the selectionization agent is the copolymer (Dow-550) of benzyl silicon and dimethyl-silicon.Catalyst after above step process is at 466 ℃, 3.55MPa, 4h
-1WHSV and H
2/ hydrocarbon is under 2 the condition, and toluene conversion is 30.9%, the paraxylene selectivity is 90.2%.
Above-mentioned method for preparing catalyst complex steps, used organosilicon are selected shape agent complex structure, are cost an arm and a leg, and solvent is carbon 10 to the high carbon alkane of carbon 12 or contains the special surface activating agent that is not easy to obtain, thereby solvent cost is higher.Catalyst needs could to obtain para-selectivity relatively preferably through dystopy selectionizations processing repeatedly, and the processing of dystopy selectionization all will be passed through two-stage roasting at every turn, and in temperature-fall period need N
2Protection.As obtaining better treatment effect, after the processing of dystopy selectionization, adopt steam treatment in addition, or the processing of carbon distribution selectionization, or original position is selected the shape finishing.So also have the selectionization of adjustment effect to be difficult to accurate prediction, operate uppity shortcoming.
Gui Shouxi etc. have announced catalyst modification method similar to the above in CN1121904, different is among the embodiment with molecular weight is that 300～4000 polysiloxanes floods zeolite.Selecting the ZSM-5 zeolite in the embodiment for use is the good Al that do not contain as activity of such catalysts component, binding agent
2O
3Silica.After sesbania powder and silica and Hydrogen ZSM-5 mixed, add water again, preferably add silica aqueous solution and mix and pinch, and then extruded moulding.For further removing the metal cation in the catalyst, the catalyst that before with the polysiloxanes dipping, preferably makes with the ammonium salt solution dipping again.Be 300-4000 polysiloxanes dipping modification 1-60 hour, filtration, drying and roasting with molecular weight then.Adopting molecular weight was that 1200 dimethicone carries out after 2 dystopys handle, 400～460 ℃ of temperature, pressure 0.5～2.0MPa, toluene feed weight space velocity 1～5 hour
-1, hydrogen and charging toluene volume ratio be that 100～500 o'clock paraxylene selectivity reach 95 heavy %, toluene conversion reaches 31%.
Owing to the viscosity of the polysiloxanes that is used for shape-selection and modification is bigger, in dipping process, polysiloxanes just can not be adsorbed on the outer surface of catalyst granules equably, easily form and pile up at the catalyst member outer surface, form inhomogeneous deposition, when causing shape-selective disproportionation reaction, catalyst selectivity and reactivity are wayward; If the polysiloxanes viscosity of impregnated catalyst is too small, molecular weight is little by 400, and the polysiloxanes that is adsorbed in the catalyst outer surface during filtration runs off easily, causes adverse effect also can for the shape-selection and modification effect of catalyst.Thereby used select that the shape polysiloxanes also needs select meticulously and owing to do not use solvent polysiloxanes large usage quantity, wayward, the whole catalyst preparation process of deposition process is still more loaded down with trivial details.
Ethyl orthosilicate is a kind of molecular weight commonly used, cheap less than 400 big molecule organo-silicon compound, and the modification that can be used for Hydrogen ZSM-5 is to improve the para-selectivity of toluene disproportionation.Forefathers also did some trials, did not all obtain ideal results.Herkes suggestion once in USP.4283306 is used repeatedly and is handled.This patent is pointed out to modify by ethyl orthosilicate and is utilized amorphous silica to make the method for crystalline silica catalyst modification, compared through the teos solution single treatment then roasting catalyst with through twice processing of this solution and the serviceability of all passing through the catalyst of roasting after each the processing.This patent is pointed out, methylation reaction with toluene reacts as index, this catalyst of Chu Liing is equal poor than single treatment on the activity and on the selectivity once more, this shows that the repeatedly ethyl orthosilicate dystopy selectionization processing of being undertaken by this method there is no benefit, has in fact reduced the efficient of catalyst in the shape selective reaction.
Wang Hui has been described in detail each with the Hydrogen ZSM/SiO of 2.0g ethyl orthosilicate/40ml ethanol solution to the 5%Ni dipping in " the selectivity toluene disproportionation on the modified zsm-5 zeolite " (Master's thesis, Fudan University, 2000)
2Carry out the method for three chemical liquid depositions.Because ethyl orthosilicate is a volatile materials, its boiling point is 176 ℃, and well below decomposition temperature, in the roasting direct process, most ethyl orthosilicates were overflowed surperficial before decomposing, and only had minute quantity to form SiO
2Coating, modification efficiency are very low.At 2.1MPa reaction pressure, 425 ℃ of temperature, toluene by weight air speed 4h
-1, H
2With the mol ratio of toluene be that the methylbenzene shape selective disproportionation para-selectivity only is 36.5wt% under 2 reaction conditions.This result is than with silicon oil modified weak effect, and uses behind this modifier modification with 100% water vapour 288-500 ℃ of processing 2 hours again, and the activity of toluene disproportionation is 26% under 500 ℃ of treatment conditions, the selectivity of paraxylene has only 70% (petrochemical industry, 29, (401), 2000).Zheng etc. are at Topics in Catalysis, adopt the big crystal grain dealuminzation of tetraethoxy silicone modification Hydrogen ZSM-5 zeolite in 22 (101), 2003, under the extremely low toluene conversion when (about 1%) selectivity of paraxylene also only be 71%.As seen no matter make the catalyst that is used for selective disproportionation of toluene that modifier obtains with said method with ethyl orthosilicate, still be aspect the conversion ratio in selectivity, all very undesirable.
Summary of the invention:
The objective of the invention is: in order to overcome loaded down with trivial details, the used organosilicon modifier price of catalyst for selective disproportionation of toluene preparation process height in the prior art, complex structure or consumption are many, solvent for use is expensive; Perhaps need to add in the catalyst precious metal and or shortcoming such as conversion ratio is low and to have proposed be easy to get cheapness, consumption of simple, the used forming agent of a kind of preparation method and modifier few, need not to carry out original position and select shape finishing and catalyst and have active highly, para-selectivity catalyst for selective disproportionation of toluene high and good stability prepares and changes the shape method.
Technical scheme of the present invention is: a kind of method for preparing toluene disproportionation zeolitic catalyst that strengthens para-selectivity may further comprise the steps successively:
A) water that extrusion aid that be the zeolite of 70-90, binding agent that weight portion is 10-30 with weight portion, weight portion is 1-10 and weight portion are 1-5 mixes, and moulding is dried, and 80-150 ℃ of drying was at 300-700 ℃ of following roasting 1-20 hour;
B) be (2-50) with above-mentioned preformed catalyst with solvent and solute weight ratio: 1 joins in the organic acid soln that concentration is 0.2-5mol/L, under the 60-120 ℃ of temperature, handle 0.5-5h, filter, spend deionised water be back, neutral back 80-150 ℃ dry 1-10 hour down;
C) the handled catalyst of step b is carried out chemical liquid deposition reaction 1-20 hour with ethyl orthosilicate in solvent under 10-90 ℃, filter then or oven dry, gained catalyst air atmosphere wore out 1-20 hour down in 80-150 ℃, was warming up to 300-700 ℃ of roasting 1-8 hour with 2-5 ℃/minute in air at last; The ethyl orthosilicate wherein and the mass ratio of solid catalyst particle are (0.05-1): 1, and the weight ratio of solvent and solid catalyst particle is (1-50): 1;
D) with post-depositional catalyst, under 0.08-0.15MPa pressure, carry out 100% steam treatment, under 150-500 ℃ of temperature, handled 1-10 hour.
Zeolite in the wherein said catalyst is the ZSM-5 zeolite of Hydrogen, and the aperture is 5-6 , its silica alumina ratio, the mol ratio that is silica and aluminium oxide is 15-200, the ZSM-5 zeolite of preferred Hydrogen, and its silica alumina ratio is 28-120, if the silica alumina ratio of ZSM-5 is too big, the gained activity of such catalysts is lower; Extrusion aid is sesbania powder, methylcellulose or citric acid; Binding agent is the alumino-silicate or the ore deposit soil of salic composition, molecular sieve, the natural zeolite of preferred diatomite, attapulgite, kaolin, the sweet soil of sheep, nonacid or weak acid; The best is the sweet soil of sheep; In order to increase the effect of ethyl orthosilicate at the outer surface chemical liquid deposition of catalyst granules, available organic acid soln is handled before deposition, organic acid is oxalic acid, formic acid, acetate, adipic acid, tartaric acid, citric acid, butanedioic acid or EDTA, preferred oxalic acid or citric acid, concentration is 0.5-2mol/L; At the chemical liquid deposition solvent for use is carbon number smaller or equal to 7 alkane, cycloalkane, aromatic hydrocarbons, the carbon number mixed liquor less than 4 low-carbon alcohols or low-carbon alcohols, preferred normal heptane, n-hexane, hexahydrotoluene, cyclohexane, benzene, toluene, 95% methyl alcohol or 95% ethanol, the best is a cyclohexane.
Wherein get the h-type zeolite ZSM-5 that weight portion is 70-85, the sweet soil of sheep that weight portion is 20-30 among the preferred steps a, other proportioning is constant.
The mass ratio of preferred ethyl orthosilicate and solid catalyst particle is (0.2-0.6): 1, and the deposition reaction temperature is 30-60 ℃, sedimentation time is 0.5-7 hour.Sintering temperature is 450～550 ℃ among the preferred steps c, and roasting time is 4～6 hours.
Can directly the sweet soil of Hydrogen ZSM-5, extrusion aid and sheep be mixed during the described preparation catalyst of the inventive method, drying and roasting after the moulding.General forming method is extrusion molding, compression forming, rotational forming.That the shape of moulding can be is cylindrical, spherical, bar shaped or cloverleaf pattern.
Above-mentioned Hydrogen ZSM-5 can directly enough buy, and also can be obtained after acid exchange or ammonium exchange roasting by NaZSM-5.NaZSM-5 can use inorganic ammonia, organic amine or direct method synthetic, and its crystal grain diameter is at the 0.1-10 micron, preferred 2-5 micron.The ammonium exchange adopts method well known to those skilled in the art to carry out, and as adopting the ammonium salt solution impregnated zeolite, promptly makes Hydrogen ZSM-5 350-550 ℃ of roasting then.
The described chemical liquid deposition modification of the inventive method is to carry out repeatedly the selection processing of dystopy with the catalyst granules of ethyl orthosilicate after to the organic acid Treatment Solution, and handles at every turn and follow-uply improve selection of catalysts and activity with roasting.This scheme is still unmanned to be proposed, and is not more than 3 chemical liquid deposition reactions again but the present invention has been found that the catalyst that will obtain; It is the catalyst that obtains through secondary selectionization processing scheme again, has suffered beyond thought excellent results at toluene disproportionation process, and ethyl orthosilicate chemical liquid deposition, roasting process are 2 times among the preferred catalyst preparation method.After each silicon modification, catalyst all needs dry aging, roasting.
Prepared as stated above catalyst granules has inside and outside SiO
2Feature pockety is by the above-mentioned as can be seen feature of sem analysis.Fig. 1, Fig. 2 and Fig. 3 are respectively the SEM figure of the twice-modified catalyst inner and outer portions of silicon and do not carry out that organic acid is handled and the SEM figure of silicon modification, Fig. 4 for the EDS electron spectrum a) located among Fig. 1, Fig. 5 to b in the corresponding figures 2) the EDS electron spectrum located.Catalyst outer layer part ZSM-5 grain contours is unintelligible as shown in Figure 2, and the surface of outer layer segment detects the existence less than the Al element, only is O and Si, can be speculated as SiO
2, SiO is described
2Unformed state with superfine granularity (about 100nm) covers on the outer field Hydrogen ZSM-5 crystal grain outer surface.And inner SEM image (Fig. 1) show the catalyst grain morphology with deposit differ less, can clearly observe the crystal grain of ZSM-5, and the EDS of catalyst inside spectrum detects the Al element and exists.These presentation of results, the SiO in the catalyst that obtains with said method
2Major sedimentary is scattered in the outer surface of the outer mesolite crystal grain of catalyst granules, the catalyst that is used for toluene disproportionation for preparing above-mentioned feature does not still have the someone and proposes, this feature makes the ethyl orthosilicate consumption more after a little while, just can obviously strengthen the para-selectivity of catalyst in toluene disproportionation.
Steam treatment can remove framework aluminum as a kind of method of modifying simple to operate in zeolite cavity, the aluminium species that removes is filled in the Hydrogen ZSM-5 duct, has increased the tortuosity in duct, thereby further improves selection of catalysts.With catalyst 100% steam treatment under normal pressure of secondary silicon modification, the preferred temperature of its treatment conditions is under 250-350 ℃, and the preferred process time is 1-3 hour.Need not to carry out further inorganic acid pickling after the steam treatment, its toluene disproportionation activity only has decline slightly, and the paraxylene selectivity brings up to more than 94% from 90%, and selectivity is up to 97% under the optimum steam treatment temperature, and concrete outcome is seen embodiment 21-24.
Catalyst with the inventive method modification is applicable to the aromatic hydrocarbons shape-selective disproportionation reaction, especially is fit to methylbenzene shape selective disproportionation and produces benzene and paraxylene.The disproportionated reaction condition comprises reaction temperature 350-500 ℃, and pressure is about 10-5000KPa (gauge pressure), is about 0.2-10 hour during with the weight sky
-1, the mol ratio of the free hydrogen of existence and raw material toluene is about (0.5-5.0): 1.
Beneficial effect
1, method for preparing catalyst of the present invention use natural ore deposit soil for binding agent, need not to add the precious metal modification, raw material cheapnesss such as used binding agent and deposition agent are easily carried, cost is low.
2, to have process simple for method for preparing catalyst of the present invention, with the modifier ethyl orthosilicate catalyst is carried out shape-selection and modification, after catalyst only need carry out processing of 1～2 dystopy selectionization and water at low temperature steam treatment, can be directly used in the methylbenzene shape-selective disproportionation reaction, need not again catalyst to be carried out the processing of original position adjustment selectionization, just can reach the toluene conversion and the paraxylene selectivity of prior art catalyst.
2, the catalyst effect of the method for the invention modification preparation is good, for example 440 ℃, 1.2MPa, toluene feed weight space velocity 3 hours
-1, H
2With toluene mole ratio be that through 218 hours running, when the toluene average conversion was 23.1% (weight), the paraxylene average selectivity reached 96.5% under 2 the condition.(seeing embodiment 17)
Description of drawings:
Fig. 1: the SEM figure of the interior layer segment of 2 ethyl orthosilicate modified catalysts.
Fig. 2: the SEM figure of the outer layer segment of 2 ethyl orthosilicate modified catalysts.
Fig. 3: the SEM figure of unmodified catalyst.
Fig. 4: the EDS figure on the internal layer surface of 2 ethyl orthosilicate modified catalysts.
Fig. 5: the EDS figure of the superficies of 2 ethyl orthosilicate modified catalysts.
Fig. 6: catalyst stability lab diagram.
The specific embodiment:
Further specify the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1 (Comparative Examples)
Present embodiment carries out the modification of chemical liquid deposition silicon with the inventive method to catalyst.
Being 38 Hydrogen ZSM-5 zeolite powder (Catalyst Factory, Nankai Univ) and the sweet soil of sheep with silica alumina ratio mixes by 80: 20 weight part ratio, is that 4 sesbania powder adds wherein again with weight portion, is fully mixed to evenly, adds 5 parts water and mixes and pinch also extruded moulding.
The solid that extruded moulding obtains dries the back 110 ℃ of dryings 3 hours, and 550 ℃ of roastings 3 hours make catalyst A.
Toluene disproportionation process carries out on the high pressure micro-reaction equipment, gets 1 gram catalyst A and is seated in 500mm length, and internal diameter is the stainless steel reaction pipe stage casing of 14mm, fills quartz sand up and down.Pure toluene charging, mass space velocity are 3.0h
-1, reaction temperature is 440 ℃, and reaction pressure is 1.2MPa, and hydrogen hydrocarbon mol ratio is 2.Before the toluene feed under 440 ℃ of temperature nitrogen activation 1h, product is cooled to liquid phase through cold-trap, gets liquid-like behind the reaction 4h, analyzes it by gas chromatograph and forms, and the results are shown in Table 1.
Paraxylene selectivity Sp (%) wherein:
Subscript: B--------------benzene
T--------------toluene
The PX-------------paraxylene
The MX-------------meta-xylene
The OX-------------ortho-xylene
Embodiment 2-5
Following examples are investigated the influence to the catalyst para-selectivity of frequency of depositing.
Get above-mentioned preformed catalyst A particle 10 grams, (20 ℃) under the room temperature, add cyclohexane solvent in 8: 1 ratio of liquid-solid mass ratio, add 2 gram ethyl orthosilicates again, under stirring condition, carry out chemical liquid deposition reaction 10 hours, drying, 110 ℃ are aging after 5 hours, in Muffle furnace, be warmed up to 550 ℃ of roastings 4 hours, get catalyst B with 2 ℃/min.
Get catalyst B particle 5 grams, add 1 gram ethyl orthosilicate under the similarity condition again and deposit, wear out and roasting, the gained catalyst is C.
Get preformed catalyst A particle 5 grams, by the modified condition of catalyst B, disposable adding 2 grams carry out silicon modification, gained catalyst D.The catalyst of embodiment 2-5 carries out toluene disproportionation by embodiment 1 reaction condition, the results are shown in Table 1.
Table 1:
| Embodiment | Catalyst | TEOS/ preformed catalyst/g/g | Toluene conversion/wt% | Paraxylene selectivity/wt% | Benzene/dimethylbenzene mol ratio |
| 1 | A | 0 | 35.5 | 25.8 | 1.1 |
| 2 | B | 0.2 | 25.5 | 81.6. | 1.3 |
| 3 | C | 0.2 secondary | 22.4 | 88.0 | 1.3 |
| 4 | D | 0.4 | 21.7 | 73.0 | 1.4 |
Table 1 data show carries out the catalyst B after the silicon modification one time to catalyst, the active reduction, but selectivity strengthens greatly, than the catalyst B of a silicon modification, catalyst C activity after the modification of secondary silicon slightly descends, but the selectivity of paraxylene further brings up to 88%.Comparing embodiment 3 and 4 can be found out same deposition, and secondary more helps improving the paraxylene selectivity than primary depositing.
Embodiment 6-11
Following examples are investigated the influence of different organic acids solution-treated zeolite activity component to catalyst activity and ethyl orthosilicate chemical liquid deposition effect
Get catalyst A particle 20 grams, adding 160 gram concentration is the oxalic acid aqueous solution of 2mol/L, refluxes under 80 ℃ of temperature and stirs 2 hours, and filtration washing, oven dry then obtains catalyst E.Get 15 gram catalyst E again, after the described method of usefulness embodiment restrained the ethyl orthosilicate modifications with 2.25, drying, aging and roasting obtained catalyst F.
Get catalyst A particle 10 grams equally, adding 40 gram concentration is the citric acid hydrous ethanol solution of 2mol/L, refluxes under 80 ℃ of temperature and stirs 2 hours, and filtration washing, oven dry then obtains catalyst G.Get 8 gram catalyst G again, after the described method of usefulness embodiment restrained the ethyl orthosilicate modifications with 1.2, drying, aging and roasting obtained catalyst H.
Get 12 gram catalyst F, after 4.8 gram ethyl orthosilicate modifications, drying, aging and roasting obtain secondary silicon modified catalyst I.
Get 6 gram catalyst H, after 2.4 gram ethyl orthosilicate modifications, drying, aging and roasting obtain secondary silicon modified catalyst J.
Catalyst E-J among the embodiment 6-11 carries out toluene disproportionation process under the reaction condition in embodiment 1, its result is as shown in table 2.
Embodiment 12 (Comparative Examples)
Get 2 gram catalyst A, after 0.3 gram ethyl orthosilicate modification, drying, aging and roasting obtain secondary silicon modified catalyst K
Table 2
| Embodiment | Catalyst | Method of modifying | Toluene conversion/wt% | Paraxylene selectivity/wt% | Benzene/dimethylbenzene mol ratio |
| 1 | A | 35.5 | 25.8 | 1.1 | |
| 6 | E | Oxalic acid treatment | 42.3 | 25.3 | 1.2 |
| 7 | F | Oxalic acid treatment, a siliceous deposits | 37.1 | 43.0 | 1.1 |
| 8 | G | Citric acid treatment | 40.0 | 25.9 | 1.1 |
| 9 | H | Citric acid treatment, a siliceous deposits | 29.3 | 59.8 | 1.3 |
| 10 | I | The oxalic acid washing, the secondary siliceous deposits | 25.7 | 91.7 | 1.6 |
| 11 | J | Citric acid treatment, the secondary siliceous deposits | 26.2 | 92.0 | 1.6 |
| 12 | K | Without acid treatment, a siliceous deposits | 32.9 | 34.8 | 1.2 |
As shown in Table 2, handle the conversion ratio can make catalyst through organic acid and improve 5-7%, after organic pickling simultaneously, the conversion ratio and the selectivity of catalyst of carrying out siliceous deposits again is better.
Embodiment 13-16
Following examples are the influence to the modification of chemical liquid deposition silicon of different binding agent kinds.
Get 80 weight portion silica alumina ratios and be the kaolin that 38 Hydrogen ZSM-5 zeolite adds 20 weight portions, adding 4 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst L1, reaction condition by embodiment 1 reacts, and experimental result sees Table 3.
Get 80 weight portion silica alumina ratios and be the attapulgite that 38 Hydrogen ZSM-5 zeolite adds 20 weight portions, adding 4 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst L2, reaction condition by embodiment 1 reacts, and experimental result sees Table 3.
Get 80 weight portion silica alumina ratios and be the Ludox that 38 Hydrogen ZSM-5 zeolite adds 20 weight portions, adding 4 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst L3, reaction condition by embodiment 1 reacts, and experimental result sees Table 3.
Table 3
| Embodiment | Catalyst | Binding agent | Toluene conversion/wt% | Paraxylene selectivity/wt% | Benzene/dimethylbenzene mol ratio |
| 13 | L1 | Kaolin | 24.6 | 91.0 | 1.6 |
| 14 | L2 | Attapulgite | 24.7 | 91.8 | 1.6 |
| 15 | L3 | Ludox | 28.1 | 88.0 | 1.7 |
| 10 | I | The sweet soil of sheep | 25.7 | 91.7 | 1.6 |
As shown in Table 4, the catalyst P 1 of used binding agent moulding, P2, P4 all have the activity and the selectivity of methylbenzene shape selective disproportionation preferably, performance is slightly low than the catalyst I performance that with the sweet soil of sheep is binding agent, is that the combination property of catalyst P 3 of binding agent is relatively poor therein with the Ludox.
Embodiment 16-18
Following examples are that the content of the sweet soil of different sheep in catalyst is to the modified catalyst Effect on Performance.
Get 90 weight portion silica alumina ratios and be the sweet soil of sheep that 38 Hydrogen ZSM-5 zeolite adds 10 weight portions, adding 4 parts of methylcellulose and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst M1, reaction condition by embodiment 1 reacts, and experimental result sees Table 4.
Get 75 weight portion silica alumina ratios and be the sweet soil of sheep that 38 Hydrogen ZSM-5 zeolite adds 25 weight portions, adding 8 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst M2, reaction condition by embodiment 1 reacts, and experimental result sees Table 4.
Get 50 weight portion silica alumina ratios and be the sweet soil of sheep that 38 Hydrogen ZSM-5 zeolite adds 50 weight portions, adding 4 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst M3, reaction condition by embodiment 1 reacts, and experimental result sees Table 4.
Table 4
| Embodiment | Catalyst | The weight portion of catalyst mesolite: the weight portion of binding agent | Toluene conversion/wt% | Paraxylene selectivity/wt% | Benzene/dimethylbenzene mol ratio |
| 16 | | 90∶10 | 30.4 | 87.0 | 1.9 |
| 10 | I | 80∶20 | 25.7 | 91.7 | 1.6 |
| 17 | M2 | 75∶25 | 25.4 | 94.0 | 1.5 |
| 18 | | 50∶50 | 15.3 | 92.4 | 1.3 |
The weight portion of binding agent is more appropriate 20-30 part as known from Table 4, and too high meeting influence selection of catalysts and benzene/dimethylbenzene mol ratio, and the decline of the mechanical strength of catalyst is bigger, and binding agent is too much, and activity of such catalysts declines to a great extent.
Embodiment 19-20
Investigate of the influence of Different Silicon aluminum ratio to modified effect.
Get 75 weight portion silica alumina ratios and be the sweet soil of sheep that 28 Hydrogen ZSM-5 zeolite adds 25 weight portions, adding 2 parts of citric acids and 3 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst n, microreactor reacts toluene disproportionation process, and the result is 25.1 heavy % for toluene conversion, the selectivity of paraxylene is 92.1 heavy %, and benzene/dimethylbenzene mol ratio is 1.7.
Get 75 weight portion silica alumina ratios and be the sweet soil of sheep that 80 Hydrogen ZSM-5 zeolite adds 25 weight portions, adding 4 parts of sesbania powder and 5 parts of water again mixes and pinches, carry out moulding then, method by embodiment 10 is carried out the silicon modification, obtain catalyst O, react toluene disproportionation process at microreactor, the result is 20.1 heavy % for toluene conversion, the selectivity of paraxylene is 93.1 heavy %, and benzene/dimethylbenzene mol ratio is 1.6.
Contain aluminium by a little visible zeolites that need only, it has acid function, acid activated centre is provided can for the disproportionated reaction of toluene, comes modification through method provided by the present invention, just can reach higher paraxylene selectivity.
Embodiment 21-24
To count gram embodiment 10 described catalyst I at 180 ℃, carry out steam treatment (100% steam) under 1 atmospheric pressure 2 hours, obtain catalyst P.Under embodiment 1 described condition, carried out a toluene disproportionation test then, drawn, the results are shown in Table 5 through steam treatment activity of such catalysts and selectivity.
The catalyst I of the multiple processing of number gram embodiment 10 at 250 ℃, is carried out steam treatment (100% steam) 2 hours under 1 atmospheric pressure, obtained catalyst Q.Carried out a toluene disproportionation test as embodiment 1 is described then, obtained, the results are shown in Table 5 through steam treatment activity of such catalysts and selectivity.
The catalyst I of the multiple processing of number gram embodiment 10 at 300 ℃, is carried out steam treatment (100% steam) 2 hours under 1 atmospheric pressure, obtained catalyst R.As described in embodiment 1, carried out a toluene disproportionation test then, obtained, the results are shown in Table 5 through steam treatment activity of such catalysts and selectivity.
The catalyst I of the multiple processing of number gram embodiment 10 at 350 ℃, is carried out steam treatment (100% steam) 4 hours under 1 atmospheric pressure, obtained catalyst S.As described in embodiment 1, carried out a toluene disproportionation test then, obtained, the results are shown in Table 5 through steam treatment activity of such catalysts and selectivity.
The catalyst I of the multiple processing of number gram embodiment 10 at 450 ℃, is carried out steam treatment (100% steam) 2 hours under 1 atmospheric pressure, obtained catalyst T.As described in embodiment 1, carried out a toluene disproportionation test then, obtained, the results are shown in Table 5 through steam treatment activity of such catalysts and selectivity.
Table 3 has been listed (embodiment 13-17) activity of such catalysts and the selectivity without (embodiment 10) of steam treatment and different condition steam treatment, to compare its activity and selectivity.
Table 5
| Embodiment | Catalyst | The steam treatment temperature | Toluene conversion/wt% | Paraxylene selectivity/wt% | Benzene/dimethylbenzene mol ratio |
| 21 | P | 180℃ | 25.6 | 92.0 | 1.6 |
| 22 | | 250 | 24.7 | 95.8 | 1.8 |
| 23 | R | 300 | 23.1 | 97.0 | 1.7 |
| 24 | S | 350 | 23.0 | 97.3 | 1.7 |
| 25 | T | 450 | 24.8 | 77.2 | 1.9 |
| 10 | I | Be untreated | 25.8 | 91.7 | 1.6 |
Through 2 hours catalyst samples in 250 ℃ (embodiment 22) or 300 ℃ (embodiment 23) or 350 ℃ of (embodiment 24) steam treatment, untreated active decline of its specific activity, but selectivity is all than steam treatment sample height not, and higher temperature steam treatment (as 450 ℃), 2 hours, 25 of embodiment caused optionally descending rapidly.
Embodiment 26
This example is pressed the reaction condition of embodiment 1 for investigating the stability of catalyst S, successive reaction more than 200 hour, and sampling is analyzed in the course of reaction, and to obtain the stability of catalyst, the result is as shown in Figure 6.
As seen from Figure 6, the prepared catalyst high stable height of the inventive method, under average 96.5% paraxylene selectivity, the toluene average conversion is more than 23%.
Embodiment 27
This example is investigated catalyst O catalytic performance at low temperatures, 420 ℃ of reaction temperatures, reaction pressure 2.5MPa, 1.5h
-1WHSV, H
2With the mol ratio of toluene be under the condition of 2-3, the reaction result of toluene disproportionation is the heavy % of toluene conversion 28.1, the paraxylene selectivity reaches 94 heavy %, the catalyst that further illustrates the method for the invention preparation also has low-temperature catalytic activity.
Claims (10)
1. method for preparing toluene disproportionation zeolitic catalyst that strengthens para-selectivity may further comprise the steps successively:
A) water that extrusion aid that be the zeolite of 70-90, binding agent that weight portion is 10-30 with weight portion, weight portion is 1-10 and weight portion are 1-5 mixes, and moulding is dried, 80-150 ℃ of drying, at 300-700 ℃ of following roasting 1-20 hour, preformed catalyst;
B) be (2-50) with above-mentioned preformed catalyst with solvent and solute weight ratio: 1 joins in the organic acid soln that concentration is 0.2-5mol/L, under the 60-120 ℃ of temperature, handles 0.5-5h, filter, spend deionised water be neutral back 80-150 ℃ dry 1-10 hour down;
C) the handled catalyst of step b is carried out chemical liquid deposition reaction 1-20 hour with ethyl orthosilicate in solvent under 10-90 ℃, filter then or oven dry, gained catalyst air atmosphere wore out 1-20 hour down in 80-150 ℃, was warming up to 300-700 ℃ of roasting 1-8 hour with 2-5 ℃/minute in air at last; Wherein the mass ratio of ethyl orthosilicate and solid catalyst particle is (0.05-1): 1, and the weight ratio of solvent and solid catalyst particle is (1-50): 1;
D) will deposit, the catalyst after the roasting, under 0.08-0.15MPa pressure, carry out 100% steam treatment, under 150-500 ℃ of temperature, handled 1-10 hour.
2. method for preparing catalyst according to claim 1 is characterized in that described zeolite is the ZSM-5 zeolite of Hydrogen, its silica alumina ratio, and promptly the mol ratio of silica and aluminium oxide is 15-200; Extrusion aid is sesbania powder, methylcellulose or citric acid; Binding agent is the alumino-silicate or the ore deposit soil of salic composition; Organic acid is oxalic acid, formic acid, acetate, adipic acid, tartaric acid, citric acid, butanedioic acid or EDTA, and concentration is 0.5-2mol/L; Solvent is a carbon number smaller or equal to 7 alkane, cycloalkane, aromatic hydrocarbons, the carbon number mixed liquor less than 4 low-carbon alcohols or low-carbon alcohols.
3. method for preparing catalyst according to claim 2, the silica alumina ratio that it is characterized in that described Hydrogen ZSM-5 zeolite is 28-120; Binding agent is molecular sieve, the natural zeolite of diatomite, attapulgite, kaolin, the sweet soil of sheep, nonacid or weak acid; Organic acid is oxalic acid or citric acid; Solvent is the ethanol of normal heptane, n-hexane, hexahydrotoluene, cyclohexane, benzene, toluene, 95% methyl alcohol or 95%.
4. method for preparing catalyst according to claim 3 is characterized in that described binding agent is the sweet soil of sheep; Solvent is a cyclohexane.
5. method for preparing catalyst according to claim 1, the weight portion that it is characterized in that h-type zeolite ZSM-5 among the step a are that the weight portion of 70-85, the sweet soil of sheep is 20-30, and other proportioning is constant.
6. method for preparing catalyst according to claim 1 is characterized in that the mass ratio of ethyl orthosilicate and solid catalyst particle is (0.2-0.6): 1, and the deposition reaction temperature is 30-60 ℃, sedimentation time is 0.5-7 hour.
7. method for preparing catalyst according to claim 1 is characterized in that sintering temperature is 450～550 ℃ of roastings among the step C, and roasting time is 4～6 hours.
8. method for preparing catalyst according to claim 1, it is characterized in that catalyst through ethyl orthosilicate chemical liquid deposition, roasting number of times for being not more than 3 times.
9. method for preparing catalyst according to claim 8 is characterized in that catalyst is 2 times through ethyl orthosilicate chemical liquid deposition, roasting number of times.
10. method for preparing catalyst according to claim 1 is characterized in that in the steps d post-depositional catalyst under 250-350 ℃ of temperature steam treatment 1-3 hour.
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