CN103804112B - A kind of method of toluene and methanol shape selective alkylation high selectivity paraxylene processed and ethene - Google Patents
A kind of method of toluene and methanol shape selective alkylation high selectivity paraxylene processed and ethene Download PDFInfo
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- CN103804112B CN103804112B CN201410069701.0A CN201410069701A CN103804112B CN 103804112 B CN103804112 B CN 103804112B CN 201410069701 A CN201410069701 A CN 201410069701A CN 103804112 B CN103804112 B CN 103804112B
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- toluene
- catalyst
- ethene
- methyl alcohol
- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 237
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 228
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 73
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000029936 alkylation Effects 0.000 title claims abstract description 26
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 claims abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 126
- 239000012530 fluid Substances 0.000 claims description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002808 molecular sieve Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 18
- 229920000728 polyester Polymers 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- -1 carbon olefin Chemical class 0.000 description 32
- 239000000463 material Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 238000007598 dipping method Methods 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 22
- 229920001296 polysiloxane Polymers 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 229910052761 rare earth metal Inorganic materials 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000011068 loading method Methods 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 150000001342 alkaline earth metals Chemical class 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 150000001447 alkali salts Chemical class 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 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 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical group [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 150000003738 xylenes Chemical class 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
Abstract
The present invention discloses a kind of method of toluene and methanol shape selective alkylation high selectivity paraxylene processed and ethene, adopt fluidized-bed reaction technique, methylbenzene methanol is co-fed, ensureing on the basis that methyl alcohol transforms completely, toluene conversion per pass is higher than 20%, in product paraxylene in dimethylbenzene selectively higher than 90%, in light component (C1-C5), ethylene selectivity is higher than 63%, ethene and propylene molar ratio are greater than 3.3, this invention can be used for, in the industrial production of toluene and methanol shape selective alkylation paraxylene processed, further can be used for the industrial production of polyester.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of toluene and methanol shape selective alkylChange the method for high selectivity paraxylene processed and ethene.
Background technology
Due to the fast development of Chemical Industry, domestic coal methanol device processed builds up in a large number in recent yearsOperation, expects the end of this year, and domestic methanol device aggregated capacity will exceed 5,000 ten thousand tons, withThis simultaneously domestic methyl alcohol demand but less than 3,000 ten thousand tons, methyl alcohol tradition downstream formaldehyde, diformazanEther and acetic acid etc. all face certain development bottleneck at present, market in urgent need be methyl alcohol open up one emergingApplication.
At present, paraxylene (PX) is produced main toluene, C9 aromatic hydrocarbons and the mixing diformazan of adoptingBenzene is raw material, produces by disproportionation, isomerization, adsorbing separation or cryogenic separation. Be subject to heating powerLearn balance control, paraxylene only accounts for 20% left and right, thing in technical process in mixed xylenesMaterial circular treatment amount is large, equipment is huge, operating cost is high. Particularly three isomers of dimethylbenzeneBoiling point differ very little, separate more difficult. Therefore, seek high selectivity and produce paraxyleneBe necessary. In recent years, lot of domestic and international patent discloses and has prepared the new of paraxyleneCircuit, the technology of wherein preparing paraxylene by methyl alcohol and toluene by methylation reaction is subject to heightDegree is paid attention to.
Ethene is mainly to produce by petroleum path, but due to the limited supply of petroleum resourcesAnd higher price, the cost of being produced ethene by petroleum resources constantly increases. In recent years, peopleStart to greatly develop alternative materials and transform the technology of ethene processed, wherein methanol dehydration generation etheneMethod has obtained good development.
PX and ethene are two kinds of base stocks of synthesizing polyester (PET), along with global polyester needsIncreasing rapidly of the amount of asking, the also cumulative year after year of demand of two kinds of required raw materials. If at oneIn reaction, taking methyl alcohol as raw material, high selectivity obtains PX and ethene simultaneously, can be effectiveUtilize methyl alcohol, supply falls short of demand can to alleviate again PX and ethene.
In recent years, many patents disclose and have produced paraxylene and alkene taking methylbenzene methanol as raw materialMethod. It is low that patent CN101456785B discloses the paraxylene coproduction processed of a kind of high selectivityThe method of carbon olefin is used a kind of catalyst producing paraxylene on fixed bed reactorsCoproduction ethene and propylene simultaneously, but in this technology, propylene content is higher, ethylene/propene moleRatio is only 1.5. Patent CN101417236A discloses a kind of alkylation of toluene methanol system pairDimethylbenzene and low-carbon alkene fluid catalyst, use this catalyst can obtain PX and etheneWith low-carbon alkenes such as propylene, but in low-carbon (LC) hydrocarbon component, the ratio of ethene is only 52.25%,And ethylene/propene molar ratio only has 1.37. Patent CN101456784B discloses a kind of firstThe method of benzene and methylating reagent paraxylene co-producing light olefins processed, patent CN10147235BThe catalyst of a kind of methylbenzene methanol paraxylene co-producing light olefins processed is disclosed, in product to twoToluene is selectively greater than 99% in xylene isomer, ethene and propylene C1 ?C5 low-carbon (LC)In alkene, be selectively greater than 90%, but in lower carbon number hydrocarbons component, the ratio of ethene is not high, is only53.89%, and ethylene/propene molar ratio is 1.44. Patent CN101780417B discloses onePlant Catalysts and its preparation method and the application of preparing paraxylene by methyl alcohol conversion and low-carbon alkene,Use this catalyst in alkylation of toluene methanol reaction, Selectivity for paraxylene is only83.58%, in lower carbon number hydrocarbons component, ethylene contents is not high yet, is only 46.28%, and ethylene/propeneMolar ratio is only 1.44.
Making a general survey of above prior art, is mainly co-producing light olefins (third when producing PXAlkene+ethene) be main, in low-carbon alkene, propylene content is too high, and ethylene/propene ratio is not high, depositsIn the problem that selectively can not get both of the selective and ethene of PX. And existing reaction is solidOn fixed bed or moving bed, carry out, wherein the shortcoming of fixed bed reaction is that heat transfer temperature control is difficult for, andOften can be because reaction carbon distribution causes catalysqt deactivation, cause reaction must frequently switch regeneration,Complicated operation; The shortcoming of moving-burden bed reactor is structure of reactor complexity, is difficult to extensive amplificationProduce, the homogeneous phase of solid particle moves down more difficult simultaneously.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of toluene and first are providedThe method of alcohol form selected methylation high selectivity paraxylene processed and ethene, its toluene conversion existsBetween 20-35%, methanol conversion is up to 100%.
For achieving the above object, the present invention adopts following technical scheme: adopt fluid bed to carry outReaction, methylbenzene methanol is co-fed, adds catalyst in course of reaction, toluene and methyl alcohol all with urgeAgent contact, toluene and methyl alcohol high selectivity are produced paraxylene, and methyl alcohol high selectivity turns simultaneouslyTurn to ethene;
Wherein, reaction temperature is 300-600 DEG C, and reaction pressure is 0-1.0MPa; Toluene and firstThe mol ratio of alcohol is (0.5-10): 1; Toluene and methyl alcohol gross mass air speed are 0.1-10h-1。
Described catalyst makes by the following method: by ZSM-5 molecular sieve, matrix materialMaterial and binding agent mixed-forming are prepared the former powder of fluid catalyst, then adopt phosphorus-containing compound waterSolution or/and rare earth metal saline solution or/and alkaline-earth metal saline solution dipping, dry, thenAdopt siloxy group compound ethanolic solution dipping, the dry catalyst that obtains; Or described catalystMake by the following method: ZSM-5 molecular sieve, host material and binding agent are mixedThe former powder of fluid catalyst is prepared in moulding, then adopts siloxy group compound ethanolic solution to soakStain, the dry catalyst that obtains.
The former powder of described fluid catalyst comprises the ZSM-5 of 20-70% by weight percentageMolecular sieve, the host material of 20-60%, the binding agent of 5-50%; In catalyst, phosphorus accounts for catalysisThe 0-15% of agent gross weight, rare earth metal accounts for the 0-10% of total catalyst weight, and alkaline-earth metal accounts forThe 0-10% of total catalyst weight, the loading of silicon after siloxy group compound ethanolic solution dippingFor the 0.01-15% of total catalyst weight.
Described phosphorus-containing compound is phosphoric acid or ammonium phosphate salt; Rare earth metal salt is rare earth metal nitric acidSalt or rare-earth metal chloride, alkali salt is alkaline earth nitrate or alkaline-earth metal chlorinationThing, SiO in described ZSM-5 molecular sieve2With Al2O3Mol ratio be (20-200): 1.
Described host material is a kind of or several in kaolin, imvite, silica, aluminium oxideKind; Binding agent is one or both in Ludox, aluminium colloidal sol.
Described alkaline-earth metal is one or more in magnesium, calcium, strontium, described rare earth metal be lanthanum,One or both in cerium; Siloxy group compound is the poly-silica of tetraethyl orthosilicate, phenyl methylOne or more in alkane, tetramethoxy-silicane.
Described reaction temperature is 400-540 DEG C.
The mol ratio of described toluene and methyl alcohol is (1-5): 1; Toluene and methyl alcohol gross mass air speedFor 1-5h-1。
The material that simultaneously enters fluid bed with toluene, methyl alcohol also comprises nitrogen and steam.
Toluene conversion is greater than 20%, and methanol conversion is that 100%, PX is selectively 90%Above, in light component, ethylene selectivity is more than 63%, and ethene and propylene molar ratio are greater than3.3。
Compared with prior art, the beneficial effect that the present invention has: the present invention is enterprising at fluid bedOK, catalyst is easily regenerated; Toluene conversion per pass is higher than 20%, methanol conversion up to100%, PX is selectively more than 90%; In light component (C1-C5), ethylene selectivity is 63%Above, the molar ratio of ethene and propylene is greater than 3.3. The present invention is directed to production of polyester required twoPlanting base stock is the feature of paraxylene and ethene, and adopting toluene and methyl alcohol is raw material, passes throughCourse of reaction high selectivity production paraxylene and ethene simultaneously, the present invention can be used for tolueneIn the industrial production of methanol shape selective alkylation paraxylene processed, further can be used for the work of polyesterIndustry is produced.
Detailed description of the invention
The present invention adopts fluid bed to react, and the charging simultaneously of toluene and methyl alcohol, identical behaviourDo under condition, produce two by course of reaction while high selectivity on a kind of catalystToluene and ethene.
Catalyst is to utilize ZSM-5 molecular sieve, host material and the preparation of binding agent mixed-formingThe former powder of fluid catalyst, then uses the phosphorus-containing compound aqueous solution or/and rare earth metal salt solutionSolution is or/and the acidity of the former powder of alkaline-earth metal saline solution regulating catalyst, then through alkoxylateCompound is modified and is eliminated the fluid catalyst that outer surface acidity obtains. In catalyst raw powderZSM-5 molecular sieve accounts for the 20-70wt% of catalyst raw powder gross weight, and host material accounts for catalystThe 20-60wt% of former powder gross weight; Binding agent accounts for the 5-50wt% of catalyst raw powder, through peracidAfter property modulation and finishing, the 0-15wt% that phosphorus content is total catalyst weight is or/and alkaline earthTenor is that the 0-10wt% of total catalyst weight is or/and rare earth metal content is that catalyst is totalThe 0-10wt% of weight; The loading that silicone compounds ethanol solution is modified rear silicon isThe 0.01-15wt% of total catalyst weight.
Catalyst preparation process is as follows:
1. by molecular screen primary powder, host material, the moulding of binding agent mixed atomizing, obtain fluid bedCatalyst raw powder.
2. former fluid catalyst powder is utilized to the phosphorus-containing compound aqueous solution and/or rare earth metal saltThe aqueous solution and/or alkaline-earth metal saline solution flood modification, obtain the catalysis of modified fluidized bedAgent.
3. adopt siloxy group compound ethanolic solution to carry out surface to modified fluidized bed catalystModify to eliminate catalyst outer surface acidity, obtain fluid catalyst. Or only adopt above-mentionedStep 1 and 3 make catalyst.
SiO in catalyst of the present invention ZSM-5 molecular sieve used2With Al2O3Mol ratio be（20-200）：1。
Catalyst of the present invention host material used is kaolin, imvite, silica, oxidationOne or more in aluminium.
Catalyst of the present invention amorphous binding agent used be a kind of in Ludox, aluminium colloidal sol orTwo kinds.
Catalyst of the present invention phosphorus-containing compound used is phosphoric acid or ammonium phosphate salt, is specially phosphorusAcid, ammonium dihydrogen phosphate (ADP), ammonium phosphate or diammonium hydrogen phosphate; Alkali salt is alkaline-earth metal nitric acidSalt or alkaline earth metal chloride, alkaline-earth metal is one or more in magnesium, calcium, strontium, rare earthSlaine is rare-earth metal nitrate or rare-earth metal chloride, and rare earth metal is in lanthanum, ceriumOne or both; Siloxy group compound is tetraethyl orthosilicate, phenyl methyl polysiloxanes, fourOne or more in methoxy silane.
The operating condition of process of the present invention is reaction mass and catalyst haptoreaction, adoptsFluid bed reacts; Reaction temperature is 300-600 DEG C, and reaction pressure is 0-1MPa; TolueneWith methyl alcohol mol ratio be (0.5-10): 1; Toluene and methyl alcohol gross mass air speed are 0.1-10h-1；The wherein preferred 400-540 DEG C of reaction temperature, toluene and methyl alcohol mol ratio be (1-5) preferably: 1, firstBenzene and the preferred 1-5h of methyl alcohol gross mass air speed-1. In it, enter fluid bed with toluene, methyl alcohol simultaneouslyMaterial also comprise nitrogen and steam.
The side that toluene of the present invention reacts high selectivity with methyl alcohol produces paraxylene and etheneMethod, in reaction, toluene and methanol alkylation generate paraxylene, and methanol conversion is ethene simultaneously;Toluene conversion per pass is higher than 20%, methanol conversion up to 100%, PX selectively 90%Above, in light component (C1-C5) ethylene selectivity more than 63%, ethylene/propene mol ratioValue is higher than 3.3.
Describe the present invention below by embodiment.
Embodiment 1
The preparation of catalyst: by 31.01kg demineralized water, 1.95kgZSM-5 molecular sieve（SiO2/Al2O3Mol ratio is 60:1), 0.71kg aluminium oxide, 2.60kg Ludox, 3.73Kg aluminium colloidal sol, roasting after mixed atomizing moulding, obtains catalyst raw powder. Get that 400g is above-mentioned to be urgedThe former powder of agent is dissolved in the solution impregnation, dry of 252g water successively with 48g diammonium hydrogen phosphate; 48gLanthanum nitrate is dissolved in the solution impregnation, dry of 252g water; 150g tetraethyl orthosilicate is dissolved in 150gThe solution impregnation of absolute ethyl alcohol, dry; The solution that 51.81g magnesium nitrate is dissolved in 254.5g water entersThe modification of row dipping, then through 120 DEG C dry, roasting obtains catalyst at 550 DEG C, be designated asMTPX。
MTPX is carried out to alkylation of toluene methanol reaction on miniature fluid bed evaluating apparatus,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minIn situation, be warming up to 600 DEG C, process after 60min, be cooled to 400 DEG C of reaction temperatures. ProfitAfter reaction system being replaced with nitrogen, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=2:1, methylbenzene methanol weight space velocity is 0.2h-1, water vapour and toluene,The mol ratio of methyl alcohol total amount is 3:1, and the nitrogen that carrier gas is 50mL/min, under condition of normal pressureCarry out, product is analyzed by online gas-chromatography, sampling point when reaction 37minAnalyse. Reaction evaluating the results are shown in table 1.
Embodiment 2
In the present embodiment, the preparation of catalyst is with embodiment 1.
MTPX is carried out to alkylation of toluene methanol reaction on miniature fluid bed evaluating apparatus,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minSituation under be warming up to 600 DEG C, process after 60min, be cooled to 450 DEG C of reaction temperatures.After utilizing nitrogen to replace reaction system, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=0.5:1, methylbenzene methanol weight space velocity is 3h-1, water vapour and toluene,The mol ratio of methyl alcohol total amount is 3:1, and carrier gas is 25mL/min nitrogen, under condition of normal pressure, carry out,Product is analyzed by online gas-chromatography, sample analysis when reaction 37min. InsteadAnswer evaluation result to list in table 1.
Embodiment 3
In the present embodiment, the preparation of catalyst is with embodiment 1.
MTPX is carried out on small-sized fluidized bed evaluating apparatus to alkylation of toluene methanol reaction,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minSituation under be warming up to 600 DEG C, process after 60min, be cooled to 480 DEG C of reaction temperatures.After utilizing nitrogen to replace reaction system, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=3:1, methylbenzene methanol weight space velocity is 2h-1, water vapour and toluene, firstThe mol ratio of alcohol total amount is 4:1, and carrier gas is 5mL/min nitrogen, under 0.1MPa condition, carry out,Product is analyzed by online gas-chromatography, sample analysis when reaction 37min. InsteadAnswer evaluation result to list in table 1.
Embodiment 4
In the present embodiment, the preparation of catalyst is with embodiment 1.
MTPX is carried out on small-sized fluidized bed evaluating apparatus to alkylation of toluene methanol reaction,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minIn situation, be warming up to 600 DEG C, process after 60min, be cooled to 480 DEG C of reaction temperatures. ProfitAfter reaction system being replaced with nitrogen, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=1:1, methylbenzene methanol weight space velocity is 2h-1, water vapour and toluene, firstThe mol ratio of alcohol total amount is 0.5:1, and carrier gas is 50mL/min nitrogen, under 0.1MPa condition, entersOK, product is analyzed by online gas-chromatography, sample analysis when reaction 37min.Reaction evaluating the results are shown in table 1.
Embodiment 5
In the present embodiment, the preparation of catalyst is with embodiment 1.
MTPX is carried out on small-sized fluidized bed evaluating apparatus to alkylation of toluene methanol reaction,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minIn situation, be warming up to 600 DEG C, process after 60min, be cooled to 500 DEG C of reaction temperatures. ProfitAfter reaction system being replaced with nitrogen, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=5:1, methylbenzene methanol weight space velocity is 4h-1, water vapour and toluene, firstThe mol ratio of alcohol total amount is 5:1, and carrier gas is 100mL/min nitrogen, under 0.2MPa condition, entersOK, product is analyzed by online gas-chromatography, sample analysis when reaction 37min.Reaction evaluating the results are shown in table 1.
Embodiment 6
In the present embodiment, the preparation of catalyst is with embodiment 1.
MTPX is carried out on small-sized fluidized bed evaluating apparatus to alkylation of toluene methanol reaction,Loaded catalyst is 10g, and fluid bed evaluating apparatus is continuing to be connected with the air of 50mL/minIn situation, be warming up to 600 DEG C, process after 60min, be cooled to 540 DEG C of reaction temperatures. ProfitAfter reaction system being replaced with nitrogen, with micro-feed pump charging. Reaction raw materials toluene:Methyl alcohol (mol ratio)=4:1, methylbenzene methanol weight space velocity is 5h-1, water vapour and toluene, firstThe mol ratio of alcohol total amount is 1:1, and carrier gas is 50mL/min nitrogen, under 0.2MPa condition, carry out,Product is analyzed by online gas-chromatography, sample analysis when reaction 37min. InsteadAnswer evaluation result to list in table 1.
The reaction evaluating result of table 1 embodiment 1-6
As can be seen from Table 1, toluene conversion is 22.73～32.52%, and methanol conversion is100%, PX is selectively more than 90%, and ethylene selectivity is more than 63%.
Embodiment 7
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then that fluid catalyst is formerPowder adopts phosphorus-containing compound aqueous solution dipping, dry; And then adopt alkoxide compound anhydrousEthanolic solution dipping, then through 120 DEG C dry, roasting obtains catalyst at 550 DEG C. Wherein,In the former powder of fluid catalyst, the percentage by weight of ZSM-5 molecular sieve is 20%, and ZSM-5SiO in molecular sieve2With Al2O3Mol ratio be 200:1; The percentage by weight of host materialBe 60%, and host material is kaolin; The percentage by weight of binding agent is 20%, andAnd bonding agent is Ludox; P elements accounts for 0.1% of total catalyst weight, and phosphorous chemical combinationThing is phosphoric acid; After silicone compounds ethanol solution dipping, the loading of silicon is that catalyst is total0.06% of weight, and silicone compounds is tetraethyl orthosilicate.
The above-mentioned catalyst making is carried out to alkylation of toluene methanol reaction, catalysis on fluid bedAgent loadings is 10g, and fluid bed heats up under the air by 50mL/min continuing to be connected with firstTo 600 DEG C, process after 60min, be cooled to 300 DEG C of reaction temperatures, after nitrogen replacement,With micro-feed pump charging. Reaction raw materials toluene: methyl alcohol (mol ratio)=7:1, toluene and firstAlcohol gross weight air speed is 8h-1, the mol ratio of water vapour and toluene, methyl alcohol total amount is 4:1, carriesGas is the nitrogen of 25mL/min, under 0MPa condition, carries out, and product is by online gas phaseChromatogram is analyzed, and sample analysis when reaction 37min, obtains dimethylbenzene and ethene.
Embodiment 8
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then that fluid catalyst is formerPowder adopts phosphorus-containing compound aqueous solution dipping, dry; Adopt again rare earth metal saline solution dipping,Dry, then adopt alkoxide compound ethanol solution dipping, after being dried at 120 DEG CRoasting at 550 DEG C, obtains catalyst. Wherein, ZSM-5 molecule in the former powder of fluid catalystThe percentage by weight of sieve is 70%, and SiO in ZSM-5 molecular sieve2With Al2O3MoleThan being 50:1; The percentage by weight of host material is 20%, and host material is silica;The percentage by weight of binding agent is 10%, and bonding agent is aluminium colloidal sol; P elements quality accounts for urges15% of agent gross weight, and phosphorus-containing compound is ammonium dihydrogen phosphate (ADP), and rare earth metal salt is nitreAcid lanthanum, and lanthanum accounts for 0.01% of total catalyst weight; Silicone compounds ethanol solutionAfter dipping, the loading of silicon is total catalyst weight 5%, and silicone compounds is phenylMethyl polysiloxane.
Above-mentioned catalyst is carried out on fluid bed to alkylation of toluene methanol reaction, Catalyst packingAmount is 10g, and fluid bed is warming up to 600 DEG C in the air situation that continues to be connected with 50mL/min,Process after 60min, keeping temperature is 600 DEG C, utilizes nitrogen to replace reaction systemAfter, with micro-feed pump charging. Reaction raw materials toluene: methyl alcohol (mol ratio)=9:1, tolueneMethyl alcohol weight space velocity is 10h-1, the mol ratio of water vapour and toluene, methyl alcohol total amount is 5:1, carriesGas is 50mL/min nitrogen, under 0.5MPa condition, carries out, and product is by online gas phaseChromatogram is analyzed, and sample analysis when reaction 37min, obtains dimethylbenzene and ethene.
Embodiment 9
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then that fluid catalyst is formerPowder adopts rare earth metal saline solution dipping, dry; Adopt again alkoxide compound absolute ethyl alcoholSolution impregnation, then through 120 DEG C dry, roasting obtains catalyst at 550 DEG C. Wherein, streamThe percentage by weight of changing ZSM-5 molecular sieve in the former powder of bed catalyst is 30%, and ZSM-5SiO in molecular sieve2With Al2O3Mol ratio be 20:1; The percentage by weight of host material is35%, and the host material mixture that is imvite; The percentage by weight of binding agent is 35%,And bonding agent is the mixture of Ludox, aluminium colloidal sol; Rare earth metal salt is lanthanum nitrate and nitric acidThe mixture of cerium, and the gross mass of lanthanum and cerium accounts for 10% of total catalyst weight; SiliconizationAfter compound dipping, the loading of silicon is total catalyst weight 10%, and silicone compounds isTetramethoxy-silicane.
The above-mentioned catalyst making is carried out to alkylation of toluene methanol reaction, catalysis on fluid bedAgent loadings is 10g, and fluid bed is warming up to continuing to be connected with under the air by 50mL/min600 DEG C, process after 60min, being down to reaction temperature is 350 DEG C, utilizes nitrogen to reaction systemAfter system is replaced, with micro-feed pump charging. Reaction raw materials toluene: methyl alcohol (mol ratio)=8:1, methylbenzene methanol weight space velocity is 0.1h-1, water vapour and toluene, methyl alcohol total amount moleThan being 3:1, carrier gas is 25mL/min nitrogen, under 1MPa condition, carries out, and product is passed throughOnline gas-chromatography is analyzed, and sample analysis when reaction 37min, obtains dimethylbenzene and secondAlkene.
Embodiment 10
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedSynthesis type is prepared the former powder of fluid catalyst, then former fluid catalyst powder is adopted to phosphoric acid hydrogenAqueous ammonium dipping, dry, and then adopt alkaline-earth metal saline solution dipping modulation fluid bedThe acidity of catalyst raw powder, adopt again after dry alkoxide compound ethanol solution dipping withEliminate the former powder outer surface acidity of fluid catalyst, after being dried, obtain catalyst. Wherein, fluidisationIn the former powder of bed catalyst, the percentage by weight of ZSM-5 molecular sieve is 25%, and ZSM-5 dividesSiO in son sieve2With Al2O3Mol ratio be 100:1; The percentage by weight of host material is25%, and host material is the mixture of kaolin, imvite, silica; Binding agentPercentage by weight is 50%, and bonding agent is aluminium colloidal sol; Phosphorus accounts for 5% of total catalyst weight,Alkali salt is magnesium chloride, and magnesium accounts for 0.1% of total catalyst weight; Silicone compounds withoutAfter water-ethanol dipping, the loading of silicon is total catalyst weight 0.01%, and silicone compoundThing is the mixture of tetraethyl orthosilicate, phenyl methyl polysiloxanes.
The above-mentioned catalyst making is carried out to alkylation of toluene methanol reaction, catalysis on fluid bedAgent loadings is 10g, and fluid bed is warming up in the air situation that continues to be connected with 50mL/min600 DEG C, process after 60min, being cooled to reaction temperature is 570 DEG C, utilizes nitrogen to reactionAfter system is replaced, with micro-feed pump charging. Reaction raw materials toluene: methyl alcohol (mol ratio)=10:1, methylbenzene methanol weight space velocity is 0.6h-1, water vapour and toluene, methyl alcohol total amount moleThan being 5:1, carrier gas is 10mL/min nitrogen, under 0.7MPa condition, carries out, and product is logicalCross online gas-chromatography and analyze, reaction sample analysis when 37min, obtain dimethylbenzene andEthene.
Embodiment 11
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedSynthesis type is prepared the former powder of fluid catalyst, then former fluid catalyst powder is adopted to phosphorus successivelyAcid hydrogen two aqueous ammonium dippings, dry, then adopt alkaline-earth metal saline solution dipping, dry;Adopt again rare earth metal saline solution to flood, be dried the acid of the former powder of modulation fluid catalystProperty, and then adopt alkoxide compound to flood to eliminate the acid of the former powder outer surface of fluid catalystProperty, after being dried, obtain catalyst. Wherein, ZSM-5 molecular sieve in the former powder of fluid catalystPercentage by weight be 60%, and SiO in ZSM-5 molecular sieve2With Al2O3Mol ratioFor 150:1; The percentage by weight of host material is 35%, and host material be imvite,The mixture of silica, aluminium oxide; The percentage by weight of binding agent is 5%, and bonding agentFor aluminium colloidal sol; Phosphorus accounts for 2% of total catalyst weight, and alkali salt is calcium nitrate, strontium nitrateMixture, and in alkali salt, the gross mass of calcium and strontium accounts for 4% of total catalyst weight,Rare earth metal salt is the mixture of lanthanum chloride and cerium chloride, and the gross mass of lanthanum and cerium accounts for catalysis10% of agent gross weight; After silicone compounds dipping, the loading of silicon is total catalyst weight15%, and silicone compounds is tetraethyl orthosilicate, phenyl methyl polysiloxanes, tetramethyl oxygenThe mixture of base silane.
The catalyst of above-mentioned preparation is carried out on fluid bed to alkylation of toluene methanol reaction, catalysisAgent loadings is 10g, and fluid bed is lower intensification in the air situation that continues to be connected with 50mL/minTo 600 DEG C, process after 60min, being down to reaction temperature is 580 DEG C, utilizes nitrogen to insteadAfter the system of answering is replaced, with micro-feed pump charging. Reaction raw materials toluene: methyl alcohol (moleThan)=6:1, methylbenzene methanol weight space velocity is 1h-1, the rubbing of water vapour and toluene, methyl alcohol total amountYou are than being 1:1, and carrier gas is 50mL/min nitrogen, carries out product under 0.8MPa conditionAnalyze by online gas-chromatography, sample analysis when reaction 37min, obtains dimethylbenzeneAnd ethene.
Embodiment 12
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then that fluid catalyst is formerPowder adopts alkaline-earth metal saline solution dipping, dry; Adopt again alkoxide compound absolute ethyl alcoholSolution impregnation to be to eliminate fluid catalyst former powder outer surface acidity, then through 120 DEG C dry,At 550 DEG C, roasting obtains catalyst. Wherein, ZSM-5 molecular sieve in the former powder of fluid catalystPercentage by weight be 25%, and SiO in ZSM-5 molecular sieve2With Al2O3Mol ratioFor 100:1; The percentage by weight of host material is 25%, and host material be kaolin,The mixture of imvite, silica; The percentage by weight of binding agent is 50%, and bonding agentFor aluminium colloidal sol; Alkali salt is magnesium nitrate, and magnesium accounts for 6% of total catalyst weight; SiliconAfter siloxane compound ethanol solution dipping, the loading of silicon is total catalyst weight0.01%, and silicone compounds is the mixing of tetraethyl orthosilicate, phenyl methyl polysiloxanesThing.
The above-mentioned catalyst making is carried out to alkylation of toluene methanol reaction, catalysis on fluid bedAgent loadings is 10g, and toluene and methyl alcohol are first warming up under the air by 50mL/min600 DEG C, process after 60min, be 570 DEG C in reaction temperature, after nitrogen replacement, with traceFeed pump charging. Reaction raw materials toluene: methyl alcohol (mol ratio)=10:1, methylbenzene methanol weightAir speed is 0.6h-1, the mol ratio of water vapour and toluene, methyl alcohol total amount is 5:1, carrier gas isThe nitrogen of 50mL/min, carries out under 0.7MPa condition, and product is by online gas-chromatographyAnalyze, sample analysis when reaction 37min, obtains dimethylbenzene and ethene.
Embodiment 13
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then adopt alkaline-earth metal salt solutionSolution by former fluid catalyst powder flood, dry, then adopt rare earth metal saline solution dipping,Dry; Adopt again alkoxide compound ethanol solution to flood to modify fluid catalyst formerPowder outer surface acidity and pore structure, then through 120 DEG C dry, roasting is urged at 550 DEG CAgent. Wherein, in the former powder of fluid catalyst, the percentage by weight of ZSM-5 molecular sieve is 60%,And SiO in ZSM-5 molecular sieve2With Al2O3Mol ratio be 150:1; Host materialPercentage by weight is 35%, and host material is the mixing of imvite, silica, aluminium oxideThing; The percentage by weight of binding agent is 5%, and bonding agent is aluminium colloidal sol; Alkali saltFor the mixture of calcium nitrate and strontium nitrate, and calcium and strontium gross mass account for total catalyst weight2%, rare earth metal salt is the mixture of lanthanum nitrate and cerous nitrate, and lanthanum and cerium gross mass account for and urge1% of agent gross weight; The loading that silicone compounds is modified rear silicon is total catalyst weight15%, and silicone compounds is tetraethyl orthosilicate, phenyl methyl polysiloxanes, tetramethylThe mixture of TMOS.
The catalyst of above-mentioned preparation is carried out to methylbenzene methanol alkane on miniature fluid bed evaluating apparatusGlycosylation reaction, loaded catalyst is 10g, miniature fluid bed evaluating apparatus is connected with continuingIn in the air situation of 50mL/min, be warming up to 600 DEG C, process after 60min, be down to reactionTemperature is 580 DEG C, after utilizing nitrogen to replace reaction system, with micro-feed pump charging.Reaction raw materials toluene: methyl alcohol (mol ratio)=6:1, methylbenzene methanol weight space velocity is 1h-1, waterThe mol ratio of steam and toluene, methyl alcohol total amount is 5:1, and carrier gas is 50mL/min nitrogen,Under 0.8MPa condition, carry out, product is analyzed by online gas-chromatography, reactionSample analysis when 37min, obtains dimethylbenzene and ethene.
Embodiment 14
The preparation of catalyst: demineralized water, ZSM-5 molecular sieve, host material and binding agent is mixedClose roasting after spray shaping, obtain the former powder of fluid catalyst, then adopt alkoxide compoundEthanol solution floods to modify the former powder outer surface acidity of fluid catalyst and pore structure, soAfter through 120 DEG C dry, roasting obtains catalyst at 550 DEG C. Wherein, fluid catalystIn former powder, the percentage by weight of ZSM-5 molecular sieve is 60%, and in ZSM-5 molecular sieveSiO2With Al2O3Mol ratio be 150:1; The percentage by weight of host material is 35%, andAnd host material is the mixture of imvite, silica, aluminium oxide; The weight percent of binding agentThan being 5%, and bonding agent is aluminium colloidal sol; The loading that silicone compounds is modified rear silicon is15% of total catalyst weight, and silicone compounds is that tetraethyl orthosilicate, phenyl methyl are poly-The mixture of siloxanes, tetramethoxy-silicane.
The catalyst of above-mentioned preparation is carried out to methylbenzene methanol alkane on miniature fluid bed evaluating apparatusGlycosylation reaction, loaded catalyst is 10g, miniature fluid bed evaluating apparatus is connected with continuingIn in the air situation of 50mL/min, be warming up to 600 DEG C, process after 60min, be down to reactionTemperature is 580 DEG C, after utilizing nitrogen to replace reaction system, with micro-feed pump charging.Reaction raw materials toluene: methyl alcohol (mol ratio)=6:1, methylbenzene methanol weight space velocity is 1h-1, waterThe mol ratio of steam and toluene, methyl alcohol total amount is 5:1, and carrier gas is 50mL/min nitrogen,Under 0.8MPa condition, carry out, product is analyzed by online gas-chromatography, reactionSample analysis when 37min, obtains dimethylbenzene and ethene.
In the present invention, adopt the phosphorus-containing compound aqueous solution or/and rare earth metal saline solution or/and alkaliEarth metal salt aqueous solution dipping, to change the acidity of the former powder of fluid catalyst, adopts siloxanesBased compound ethanolic solution dipping is in order to modify and to eliminate the former powder appearance of fluid catalystThe acidity of face and pore structure.
The present invention adopts fluidized-bed reaction technique, and methylbenzene methanol is co-fed, is ensureing methyl alcohol 100%On the basis transforming, toluene conversion per pass exceedes 20%, and in product, paraxylene is at dimethylbenzeneIn selectively higher than 90%, in light component (C1-C5) ethylene selectivity higher than 63%, secondAlkene/propylene molar ratio is higher than 3.3, and this invention can be used for toluene and methanol shape selective alkylation system pairIn the industrial production of dimethylbenzene, further can be used for the industrial production of polyester.
Claims (5)
1. the side of a toluene and methanol shape selective alkylation high selectivity paraxylene processed and etheneMethod, is characterized in that, adopts fluid bed to react, and methylbenzene methanol is co-fed, course of reactionIn add catalyst, toluene all contacts with catalyst with methyl alcohol, toluene and methyl alcohol high selectivity are rawProduce paraxylene, methyl alcohol high selectivity is converted into ethene simultaneously;
Wherein, reaction temperature is 300-600 DEG C, and reaction pressure is 0-1.0MPa; Toluene and firstThe mol ratio of alcohol is (0.5-10): 1; Toluene and methyl alcohol gross mass air speed are 0.1-10h-1；
Described catalyst makes by the following method: by 31.01kg demineralized water, 1.95kgZSM-5 molecular sieve, SiO2/Al2O3Mol ratio is 60:1,0.71kg aluminium oxide, 2.60kgLudox, 3.73kg aluminium colloidal sol, roasting after mixed atomizing moulding, obtains catalyst raw powder;Get the above-mentioned catalyst raw powder of 400g is dissolved in 252g water successively solution with 48g diammonium hydrogen phosphateDipping, dry; 48g lanthanum nitrate is dissolved in the solution impregnation, dry of 252g water; 150g siliconAcid tetra-ethyl ester is dissolved in the solution impregnation, dry of 150g absolute ethyl alcohol; 51.81g magnesium nitrate is dissolved inThe solution of 254.5g water floods modification, then through 120 DEG C dry, roasting obtains at 550 DEG CArrive.
2. toluene according to claim 1 and methanol shape selective alkylation high selectivity system are to twoThe method of toluene and ethene, is characterized in that, described reaction temperature is 400-540 DEG C.
3. toluene according to claim 1 and methanol shape selective alkylation high selectivity system are to twoThe method of toluene and ethene, is characterized in that, the mol ratio of described toluene and methyl alcohol is (1-5):1; Toluene and methyl alcohol gross mass air speed are 1-5h-1。
4. toluene according to claim 1 and methanol shape selective alkylation high selectivity system are to twoThe method of toluene and ethene, is characterized in that, enters the thing of fluid bed with toluene, methyl alcohol simultaneouslyMaterial also comprises nitrogen and steam.
5. high according to toluene and methanol shape selective alkylation described in any one in claim 1-4The method of selective paraxylene processed and ethene, is characterized in that, toluene conversion is greater than 20%,Methanol conversion be 100%, PX selectively more than 90%, ethylene selectivity in light componentMore than 63%, ethene and propylene molar ratio are greater than 3.3.
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| CN105198691A (en) * | 2015-09-08 | 2015-12-30 | 山东成泰化工有限公司 | Synthesis method for p-xylene |
| CN108794290B (en) * | 2017-04-27 | 2020-09-04 | 中国科学院大连化学物理研究所 | In-situ and on-line preparation method of catalyst for preparing p-xylene by toluene and methanol alkylation |
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