CN101417236B - A fluidized-bed catalyst for producing p-xylene and light olefins by alkylation of toluene with methanol - Google Patents
A fluidized-bed catalyst for producing p-xylene and light olefins by alkylation of toluene with methanol Download PDFInfo
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- CN101417236B CN101417236B CN2007101762746A CN200710176274A CN101417236B CN 101417236 B CN101417236 B CN 101417236B CN 2007101762746 A CN2007101762746 A CN 2007101762746A CN 200710176274 A CN200710176274 A CN 200710176274A CN 101417236 B CN101417236 B CN 101417236B
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- xylene
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- toluene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000029936 alkylation Effects 0.000 title claims description 11
- 238000005804 alkylation reaction Methods 0.000 title claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title abstract description 27
- 150000001336 alkenes Chemical class 0.000 title description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 28
- 239000010457 zeolite Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract 4
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- -1 siloxane compound Chemical class 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000002843 nonmetals Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 150000003738 xylenes Chemical class 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 238000011935 selective methylation Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005034 decoration Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CTNCAPKYOBYQCX-UHFFFAOYSA-N [P].[As] Chemical compound [P].[As] CTNCAPKYOBYQCX-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst used for preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol, which is obtained by the modification of zeolite molecular sieve by metal, nonmetal or/and rare earth metal, mixing, spraying, drying and forming of amorphous adhesive containing silicon or aluminium and the zeolite molecular sieve, and decoration of surface acidity and porous structure by siloxane-based compounds, wherein, the content of the alkaline earth metal is 0.1-8wt percent of the total weight of the catalyst, the content of the nonmetal is 0.1-8wt percent of the total weight of the catalyst, the content of the rare earth metal is 0.1-5wt percent of the total weight of the catalyst, and the loading of the Si decorated by the siloxane-based compound is 0.1-10wt percent of the total weight of the catalyst; the catalyst is used for the reaction of preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol; in the products, the selectivity of the para-xylene in the xylene isomers is more than 99 percent and the selectivity of the ethane and propylene in the composition C1-C5 is more than 90 percent.
Description
Technical field
The present invention relates to a kind of alkylation of toluene methanol high selectivity system paraxylene and low-carbon alkene fluid catalyst.It is characterized in that methylbenzene methanol can carry out alkylated reaction and methanol decomposition reaction high selectivity simultaneously and generate paraxylene and ethene, propylene on this catalyst.
Background technology
Paraxylene and ethene are two kinds of base stocks of synthesizing polyester (PET).At present, toluene, C are mainly adopted in paraxylene production
9Aromatic hydrocarbons and mixed xylenes are raw material, produce through disproportionation, isomerization, adsorbing separation or cryogenic separation.Because the paraxylene content in its product is controlled by thermodynamics, paraxylene is at C
8Only account in the BTX aromatics about 20%, material circular treatment amount is big in the technical process, and equipment is huge, and operating cost is high.Particularly the boiling point of three isomers of xylenes differs very little, adopts common distillation technique can not obtain the high-purity paraxylene, and must adopt expensive adsorptive separation technology.Ethene be with crude refining light oil (naphtha and light diesel fuel) and liquefied petroleum gas (LPG) and the natural gas processing ethane and the propane that make be that raw material is produced, mainly depend on petroleum resources.Along with increasing rapidly of global polyester demand, the demand of required two kinds of base stock paraxylene and ethene is cumulative year after year also.
In recent years, domestic and international many patents disclose the new way of paraxylene and ethylene production, and the paraxylene that wherein toluene methylation can the production high selectivity, preparing light olefins from methanol are that non-petroleum path is produced ethene and propylene.USP 3,965, and 207 disclose use ZSM-5 molecular sieve makees catalyst, reaction temperature 500-750 ℃, are about 90% in the high selectivity of 600 ℃ of paraxylene; USP3,965,208 use the element modified ZSM-5 molecular sieve of VA to make catalyst, have suppressed the generation of meta-xylene, mainly generate paraxylene and ortho-xylene, are about 90% in the high selectivity of 600 ℃ of paraxylene; USP 4,250, and 345 use the ZSM-5 molecular sieve of phosphorus and the modification of magnesium dual element to be catalyst, are about 98% in the best selective of 450 ℃ of paraxylene; USP 4,670, and 616 use borosilicate molecular sieve and silica or aluminium oxide to be prepared into catalyst, paraxylene selectivity formula 50-60%; USP4,276,438,4,278,827 use the molecular sieve (SiO of special construction
2/ Al
2O
3>=12) also with modifications such as copper, silver, gold or germanium, tin, lead, can obtain the p dialkyl benzene of high selectivity; USP 4,444, and 989 use the pure silicon molecular sieve of crystal type, and make the compound of arsenic phosphorus, magnesium, boron and tellurium carry out modification, have improved the selectivity of paraxylene; USP 4,491, and 678 use crystal type borosilicate and IIA and IIIA element and silicon and phosphorus can improve the selectivity of paraxylene greatly and can improve life of catalyst as common component.USP 5,034, and 362 use SiO
2/ Al
2O
3>=12 ZSM-5 and ZSM-11 are catalyst, and carry out roasting being higher than under 650 ℃ the condition, can improve the selectivity of p dialkyl benzene.USP 5,563, and 310 use the acidic molecular sieve that contains the IVB element also to carry out modified catalyst with the metal of VIB, can improve the selectivity of the p dialkyl benzene of alkylation of toluene methanol reaction; USP6,504,072 use the preferred ZSM-5 of mesoporous molecular sieves, and in the steam processing down that is higher than 950 ℃, carry out modification with phosphorous oxides then, and the diffusion effect that has proposed the catalyst micropore optionally influences paraxylene; USP 6,613, and 708 use organo-metallic compound that catalyst is carried out modification, can improve the selectivity of p dialkyl benzene greatly.On the other hand, domestic and international many patents disclose the technology that non-petroleum path such as utilizing methyl alcohol or dimethyl ether is produced ethene and propylene.Mobil Oil company in 1976 has carried out methyl alcohol is converted into hydrocarbon on the ZSM-5 molecular sieve catalyst reaction.USP4 discloses methyl alcohol transforms gasoline on the ZSM-5 molecular sieve catalyst process in 035,430; USP4 discloses methyl alcohol is produced low-carbon alkene on the ZSM-5 molecular sieve catalyst technology in 542,252; USP 3,911,041, and USP 4; 049,573, USP 4,100; 219, JP 60-126233, JP 61-97231 discloses among the JP 62-70324 and EP 6501 and has used the reaction of the ZSM-5 molecular sieve catalyst of phosphorus, magnesium, silicon or alkali metal modification by preparing low carbon olefinic hydrocarbon with methanol; USP 5,367, disclose the reaction that Dalian Chemical Physics Research Institute uses the ZSM-5 molecular sieve catalyst of phosphorus and lanthanum modification to produce low-carbon alkene by methyl alcohol or dimethyl ether in 100, and the overall selectivity of its ethene, propylene and butylene can reach about 85%.
Above-mentioned patent discloses the new way of preparation paraxylene and low-carbon alkene respectively; Because two courses of reaction are acid catalyzed reaction; All require the shape selective catalysis effect; Therefore all used the modified HZSM-5 molecular sieve as the activity of such catalysts component, but because the purpose product is different, there is very big difference again in the characteristics of the catalyst of two processes.A kind of catalyst of preparation satisfies the requirement of alkylation of toluene methanol system paraxylene and methanol-to-olefins simultaneously if employ new technology, and just can be implemented in the course of reaction and produces paraxylene and ethene simultaneously.
On the other hand; Alkylation of toluene methanol system paraxylene and be that the reaction for preparing light olefins from methanol of catalyst all adopts fixed bed reaction with the ZSM-5 molecular sieve; Because the reaction carbon deposit causes catalysqt deactivation, so fixed bed reaction must frequently switch regeneration, complicated operation.
Summary of the invention
The object of the present invention is to provide a kind of alkylation of toluene methanol high selectivity system paraxylene and low-carbon alkene fluid catalyst.
For realizing above-mentioned purpose; Alkylation of toluene methanol system paraxylene provided by the invention and low-carbon alkene fluid catalyst; Be by metal, nonmetal with the former powder of zeolite molecular sieve or/and rare-earth metal modified; With the amorphous binding agent mixed atomizing drying and moulding of siliceous or aluminium, obtain through compound-modified surface acidity of siloxy group and pore structure more then; Wherein:
Alkaline earth metal content is the 0.1-8wt% of total catalyst weight;
Nonmetal content is the 0.1-8wt% of total catalyst weight;
Rare earth metal content is the 0.1-5wt% of total catalyst weight;
The loading of the compound-modified back of siloxy group Si is the 1-10wt% of total catalyst weight.
Described catalyst, wherein zeolite molecular sieve is alumino-silicate or the Silicophosphoaluminaand with crystallization skeleton structure, structure type is MFI, MEL or AEL.
Described catalyst, wherein alumino-silicate is that ZSM-5 is or/and ZSM-11 zeolite molecular sieve, preferably ZSM-5; Silicophosphoaluminaand is the SAPO-11 molecular sieve.
Described catalyst, wherein metal is alkaline-earth metal Mg, Ca oxide or its soluble-salt; Nonmetal is phosphorous oxides or phosphoric acid; Rare earth metal is the soluble-salt of lanthanum.
Described catalyst, wherein the siloxy group compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The mixture of one or more that described catalyst, amorphous binding agent wherein siliceous or aluminium are kaolin, clay, aluminium oxide, aluminium colloidal sol, silica and Ludox.
Described catalyst, wherein catalyst is the micro-spherical catalyst of spray shaping.
Catalyst of the present invention is used for producing paraxylene and low-carbon alkene reaction in the alkylation of toluene methanol high selectivity: in fluidized-bed reactor, its reaction temperature is 350-550 ℃, and preferable temperature is 400-500 ℃.
The specific embodiment
Catalyst of the present invention is to be that MFI, MEL or AEL alumino-silicate or Silicophosphoaluminaand are active component with the structure type with crystallization skeleton structure; Amorphous binding agent mixed-forming with siliceous or aluminium; Through silicone agent its outer surface acidity and duct are modified and be prepared into catalyst, its preparation process is following:
1) the former powder of zeolite molecular sieve is prepared into acidic zeolite through exchange, roasting.
2) with acidic zeolite impregnating metal, nonmetal or rare earth metal, obtain modified catalyst.
3) modified catalyst is mixed the back spray drying forming with the amorphous binding agent of siliceous or aluminium, obtain microspherical catalyst.
4) use siloxy group reagent that microspherical catalyst is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain fluidized catalyst.
The used zeolite molecular sieve of the present invention is Si-Al molecular sieve or aluminium silicophosphate molecular sieve, and Si-Al molecular sieve can be selected ZSM-5 for use, the ZSM-11 zeolite molecular sieve; Silicon phosphorus aluminium series molecular sieve can be selected the SAPO-11 molecular sieve for use.
Catalyst of the present invention carries out modification through metal, oxide, soluble-salt nonmetal or rare earth metal to acidic zeolite, and purpose is to improve the reactivity worth of catalyst preparing light olefins from methanol.
The catalyst characteristics of the present invention's preparation is shown in the following general formula of siloxy group compound:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The catalyst applications of the present invention's preparation is produced paraxylene and low-carbon alkene reaction in the methylbenzene methanol reaction, and its range of reaction temperature is 350-550 ℃, and preferable temperature range is 400-500 ℃.
The abrasion index of fluid catalyst of the present invention is less than 2.
Catalyst applications of the present invention is produced paraxylene and low-carbon alkene (ethene and propylene) reaction in the methylbenzene methanol reaction, can be through regulating the productive rate that toluene and methanol (mol ratio) ratio changes paraxylene and low-carbon alkene.The selectivity of paraxylene in xylene isomer is greater than 99% in the product, and ethene and propylene are at C
1-C
5Selectivity is greater than 90% in the component.
Through embodiment the present invention is detailed below.
Embodiment 1 (preparation Mg-HZSM-5 fluidized catalyst)
With the former powder (SiO of ZSM-5 zeolite molecular sieve
2/ Al
2O
3=61) remove template 550 ℃ of following roastings, in 80 ℃ of water-baths, exchange 4 times with ammonium nitrate solution, the exchange back obtains the HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours.
Use slaine that the HZSM-5 zeolite molecular sieve is carried out modification, step is respectively:
(1) HZSM-5 zeolite molecular sieve 10kg, 9%Mg (MgCl
26H
2O) dipping spends the night, and after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Mg-HZSM-5 zeolite molecular sieve;
(2) the Mg-HZSM-5 zeolite molecular sieve that step 1 is obtained mixes with siliceous or al binder and carries out spray drying forming: 40%Mg-HZSM-5 (butt)+20%Al
2O
3(boehmite)+40%Al
2O
3(aluminium colloidal sol)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.4, obtains the Mg-HZSM-5 fluidized catalyst of microspheroidal;
(3) use the silicone agent tetraethyl orthosilicate that the Mg-HZSM-5 fluid catalyst that step 2 obtains is carried out finishing: 5kg Mg-HZSM-5 fluidized catalyst is put into 5kg tetraethyl orthosilicate dipping and is spent the night; Incline liquid after; After 120 ℃ of oven dry; 550 ℃ of roastings 3 hours, obtain modifying back Mg-HZSM-5 fluidized catalyst, be numbered TMFC-01.
Embodiment 2 (preparation Ca-HZSM-5 fluidized catalyst)
(1) HZSM-5 zeolite molecular sieve 10kg, 9%Ca (CaCl
2) flood and spend the night, after the oven dry,, obtain the Ca-HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours;
(2) the Ca-HZSM-5 zeolite molecular sieve that step 1 is obtained mixes with siliceous or al binder and carries out spray drying forming: 40%Ca-HZSM-5 (butt)+20%Al
2O
3(boehmite)+40% kaolin+an amount of biogum, making beating, glue grind, go bubble, spray drying forming; Catalyst particle size distribution 20～100 μ m; 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.2, obtains microspheroidal Ca-HZSM-5 fluidized catalyst;
(3) use the silicone agent tetraethyl orthosilicate that the Ca-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing.Step is respectively: 5kg Ca-HZSM-5 microspherical catalyst is put into 5kg tetraethyl orthosilicate dipping spends the night, incline liquid after, after 120 ℃ of oven dry; Use solvent wash; 550 ℃ of roastings 3 hours, obtain modifying back Ca-HZSM-5 fluidized catalyst, be numbered TMFC-02.
Embodiment 3 (preparation P-HZSM-5 fluidized catalyst)
(1) HZSM-5 zeolite molecular sieve 20kg, 3%P (H
3PO
4) flood and spend the night, after the oven dry,, obtain the P-HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours;
(2) 5kg P-HZSM-5 zeolite molecular sieve is mixed with siliceous or al binder carry out spray drying forming, step is respectively: 40%P-HZSM-5 (butt)+20%Al
2O
3(boehmite)+40%SiO
2(Ludox)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.8, obtains the P-HZSM-5 fluidized catalyst of microspheroidal;
(3) use the silicone agent tetraethyl orthosilicate that the P-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing; Step is respectively: 5kg P-HZSM-5 microspherical catalyst is put into 5kg tetraethyl orthosilicate dipping spends the night, incline liquid after, after 120 ℃ of oven dry; Use solvent wash; 550 ℃ of roastings 3 hours, obtain modifying back P-HZSM-5 fluidized catalyst, be numbered TMFC-03.
Embodiment 4 (preparation P-La-HZSM-5 fluidized catalyst)
(1) gets the P-HZSM-5 zeolite molecular sieve 10kg that step 1 prepares among the embodiment 3,3%La (La (NO
3)
36H
2O) dipping spends the night, and after the oven dry, 550 ℃ of following roastings 3 hours, obtains the P-La-HZSM-5 zeolite molecular sieve;
(2) the P-La-HZSM-5 molecular sieve is mixed with siliceous or al binder carry out spray drying forming, step is respectively: 40%P-La-HZSM-5 (butt)+20%Al
2O
3(boehmite)+40%SiO
2(Ludox)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.7, obtains the P-La-HZSM-5 fluidized catalyst;
(3) use the silicone agent tetraethyl orthosilicate that the P-La-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing; Step is respectively: 5kg P-La-HZSM-5 is put into 5kg tetraethyl orthosilicate dipping spends the night, incline liquid after, after 120 ℃ of oven dry; Use solvent wash; 550 ℃ of roastings 3 hours, obtain modifying back P-La-HZSM-5 fluidized catalyst, be numbered TMFC-04.
Embodiment 5 (reaction evaluating)
Be reflected in the medium-sized circulating fluid bed reaction device and carry out.Reaction condition is following: loaded catalyst is 5Kg, and the reactor reserve is 1.5Kg, and the catalyst circulation amount is 0.1-5Kg/hr; Reaction temperature is 450 ℃; 600 ℃ of regeneration gas temperature, raw material toluene: methyl alcohol (mol ratio)=2: 1, methylbenzene methanol weight space velocity are 2 hours-1.Adopt Varian 3800 gas-chromatographies, CP-WAX 52CB capillary chromatographic column on-line analysis products distribution (normalization behind the removal toluene), as shown in table 1.C wherein
1-C
5Composition analysis adopts Varian 3800 gas-chromatographies, CP-PoraPLOT Q-HT capillary chromatographic column, and the result is as shown in table 2.
Table 1
| Catalyst | TMFC-01 | TMFC-02 | TMFC-03 | TMFC-04 |
| Feed time (min) | ?120 | ?120 | ?120 | ?120 |
| Toluene conversion (%) | ?13.75 | ?13.72 | ?16.81 | ?20.10 |
| Paraxylene selectivity (%) * | ?85.91 | ?87.67 | ?94.29 | ?99.10 |
| Products distribution (%) | ||||
| C 1-C 5 | ?6.60 | ?5.97 | ?16.53 | ?28.99 |
| Benzene | ?6.40 | ?7.14 | ?0.83 | ?0.08 |
| Ethylbenzene | ?2.65 | ?1.89 | ?0.35 | ?0.24 |
| Paraxylene | ?65.30 | ?62.93 | ?70.41 | ?64.39 |
| Meta-xylene | ?9.04 | ?7.59 | ?2.41 | ?0.00 |
| Ortho-xylene | ?1.68 | ?1.25 | ?1.85 | ?0.60 |
| ≥C 9 | ?8.34 | ?13.23 | ?7.62 | ?5.70 |
| Add up to | ?100.00 | ?100.00 | ?100.00 | ?100.00 |
*The selectivity of paraxylene in xylene isomer
Table 2
| Catalyst | TMFC-01 | TMFC-02 | TMFC-03 | TMFC-04 |
| Feed time (min) | 120 | 120 | 120 | 120 |
| CH 4 | 4.65 | 5.70 | 6.87 | 1.32 |
| C 2H 4 | 47.27 | 46.35 | 49.98 | 52.52 |
| C 2H 6 | 1.04 | 0.92 | 0.90 | 0.05 |
| C 3H 6 | 32.01 | 35.83 | 32.40 | 38.43 |
| C 3H 8 | 5.60 | 2.39 | 1.92 | 0.31 |
| C 4 + | 7.05 | 7.25 | 7.02 | 5.97 |
| C 5 + | 2.39 | 1.55 | 0.90 | 1.40 |
| C 2H 4+C 2H 6 | 79.28 | 82.18 | 82.32 | 90.95 |
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| US9486796B2 (en) * | 2009-10-08 | 2016-11-08 | Basf Se | Process for producing an si-bonded fluidized-bed catalyst |
| CN102372584B (en) * | 2010-08-23 | 2014-07-23 | 中国石油化工股份有限公司 | Fluidized catalytic method for preparing p-xylene by alkylating aromatic hydrocarbon |
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