CN110026234A - A kind of alkylation catalyst and its preparation method and application - Google Patents
A kind of alkylation catalyst and its preparation method and application Download PDFInfo
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- CN110026234A CN110026234A CN201910356171.0A CN201910356171A CN110026234A CN 110026234 A CN110026234 A CN 110026234A CN 201910356171 A CN201910356171 A CN 201910356171A CN 110026234 A CN110026234 A CN 110026234A
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 230000029936 alkylation Effects 0.000 title claims abstract description 37
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 176
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002808 molecular sieve Substances 0.000 claims abstract description 46
- 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 44
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000012808 vapor phase Substances 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- -1 phosphorus modified molecular sieves Chemical class 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 claims 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- 230000001404 mediated effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 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 description 2
- 239000002245 particle Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000009850 completed effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of alkylation catalyst and preparation method thereof and the purposes in methanol and benzene vapor phase alkylation production BTX aromatics, the catalyst be prepare with the following method: by nano-ZSM-5 molecular sieve it is powder-modified after, extruded moulding is mediated with binder, then dry and roasting；Wherein, modified nano-ZSM-5 molecular sieve powder content is 10wt%~50wt%, and the content of binder is 50wt%~90wt%；It include the P of 1.0wt%~8.0wt% in modified nano-ZSM-5 molecular sieve powder2O5With the La of 1.0wt%~5.0wt%2O3, remaining is nano-ZSM-5 molecular sieve.The catalyst, which is applied to have in methanol and benzene vapor-phase alkylation production BTX aromatics, is alkylated high-efficient, the good feature of anti-carbon performance.
Description
Technical field
The present invention relates to a kind of catalyst of chemosynthesis reaction, raw more particularly to a kind of methanol and benzene vapor-phase alkylation
Produce the catalyst and preparation method thereof of BTX aromatics.
Background technique
In recent years, caused by as the expansion of reformer scale, the increase of ethylene yield and because of steel industry development
Coking industry is greatly developed, and the production capacity of benzene sharply increases, and causes benzene excessive.Meanwhile as synthesising gas systeming carbinol technology is got over
Come more mature, the production cost of methanol reduces, and yield is significantly increased, and methanol is superfluous serious.In order to dissolve superfluous production capacity benzene and
Methanol, the alkylated technology for studying methanol and benzene are gradually risen.
Benzene and methanol alkylation are tandem reactions, and reaction first generates toluene, and toluene and methanol continue alkylation and then generates two
Toluene, and then the BTX aromatics such as multi-methyl benzene are generated, while also occurring that between product and product, between product and reactant
Parallel side reaction, such as generate ethylbenzene, propyl benzene, the first and second benzene.Therefore toluene is most in product, and dimethylbenzene takes second place, both products
It is important chemical raw material.Wherein, toluene can be used for synthesizing toluene di-isocyanate (TD.I), phenol, nitrotoleune, benzoic acid, saccharin, conjunction
At the raw material of the chemicals such as terylene, resin；Dimethylbenzene is good solvent, and paraxylene contained therein is that good polyester is former
Material.
ZSM-5 molecular sieve has been widely used in the reaction such as aromatisation, isomerization, alkylation since synthesis.Due to ZSM-5
With very strong alkylation performance and good hydrothermal stability, and can industrialized production, therefore in methanol and benzene alkyl
Changing is also preferred catalyst in the research of reaction.But in the reaction that methanol participates in, use ZSM-5 molecular sieve as catalyst
The side reactions such as MTO, MTG inevitably occur, to reduce the utilization rate of methanol.The side reactions such as MTO, MTG simultaneously easily cause
One of the main reason for catalyst carbon deposition, this is also molecular sieve catalyst inactivation.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of methanol and benzene vapor-phase alkylation
The catalyst and preparation method thereof of BTX aromatics is produced, which is applied to methanol and benzene vapor-phase alkylation produces BTX aromatics
In have be alkylated high-efficient, the good feature of anti-carbon performance, for solving the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention obtains by the following technical programs.
Present invention firstly provides a kind of alkylation catalyst, the catalyst is to prepare with the following method: will be received
After rice ZSM-5 molecular sieve is powder-modified, extruded moulding is mediated with binder, then dry and roasting；
Wherein, modified nano-ZSM-5 molecular sieve powder content is 10wt%~50wt%, and the content of binder is
50wt%~90wt%；
It include the P of 1.0wt%~8.0wt% in modified nano-ZSM-5 molecular sieve powder2O5With 1.0wt%~
The La of 5.0wt%2O3, remaining is nano-ZSM-5 molecular sieve.
Preferably, the crystal grain diameter of nano-ZSM-5 molecular sieve is 5nm~350nm, preferably 50nm~300nm.Nanoscale
ZSM-5 molecular sieve possesses bigger specific surface area and Micropore volume, and appearance carbon ability is stronger, is conducive to the anti-carbon for improving catalyst
Performance；Crystal grain is small and uniform nano-ZSM-5 molecular sieve, is conducive to the preparation stability for improving catalyst, and then reacted
The stable catalyst of performance.
Preferably, SiO in nano-ZSM-5 molecular sieve2With Al2O3Molar ratio be 50~500, wherein SiO2Molal quantity
It is to be obtained by the molal quantity conversion of Si element in nano-ZSM-5 molecular sieve, Al2O3Molal quantity be by nano-ZSM-5 molecule
The molal quantity of Al element, which converts, in sieve obtains.Molecular sieve silica alumina ratio possesses suitable acid ratio in the application, is conducive to control
The carbon deposition rate of catalyst improves the anti-carbon performance of catalyst.
Preferably, P in catalyst2O5Presoma be selected from one or both of phosphoric acid and ammonium dihydrogen phosphate.In catalyst
Middle addition P elements are inserted into molecular sieve alumina key by aluminium element, form new phosphorus alumina key, change the property selected of catalyst
Matter.The insertions of P elements reduces the acid strength of catalyst so that the original strong acid site B is transformed to two weak acid sites B,
Therefore, the probability that the side reactions such as MTO, MTG occur for methanol reduces, and improves the alkylation efficiency of methanol.
Preferably, La in catalyst2O3Presoma be lanthanum nitrate.Addition lanthanum element changes on the basis of P elements are modified
Property, modulation further is carried out to the acid of catalyst, most of strong acid center is covered, retains weak acid center, reduce MTO and
The generation of the side reactions such as MTG improves the alkylation efficiency of catalyst.
Preferably, the binder is selected from one of aluminium oxide, Aluminum sol and aluminum phosphate or a variety of.The alkane of methanol and benzene
Glycosylation reaction only needs a small amount of activated centre can be completed, and reactivity will not be reduced by adding suitable binder, on the contrary, addition is viscous
The catalyst structure stability for tying agent is more preferable, is conducive to the service life for improving catalyst.
Second aspect of the present invention additionally provides the preparation method of catalyst described above, includes the following steps:
1) it disperses nano-ZSM-5 molecular sieve in the aqueous solution of phosphorus-containing compound and is stirred to react, remove after reaction
Moisture in reaction solution obtains phosphorous white powder；
2) it roasts the phosphorous white powder to obtain phosphorus modified molecular sieves；
3) it disperses the phosphorus modified molecular sieves in the aqueous solution containing lanthanum compound and is stirred to react, remove after reaction
Moisture in reaction solution obtains white powder containing lanthanum；
4) white powder containing lanthanum is roasted to obtain lanthanum-phosphorus modified molecular sieves；
5) lanthanum-phosphorus modified molecular sieves are uniformly mixed with binder, after kneading extruded moulding, obtain alkyl through drying, roasting
Change catalyst.
Preferably, the concentration of the aqueous solution of phosphorus-containing compound is 0.10mol/L~0.50mol/L.
Preferably, the concentration of the aqueous solution containing lanthanum compound is 0.05mol/L~0.30mol/L.
The reaction that P elements are added in the application need to carry out at low temperature, and remove moisture at low temperature.In molecular sieve
Aluminium element is in acidic aqueous solution, under high temperature environment, easily by acid attack, aluminium element is caused to remove from framework of molecular sieve, made
Acidic zeolite decline is obtained, to reduce the activity of catalyst.Therefore, add P elements reaction should in a mild condition into
Row.Preferably, reaction temperature is no more than 80 DEG C in step 1).Preferably, step 1) and/or 3) in, using negative pressure remove dereaction
Moisture in liquid.
Preferably, step 2) and/or 4) in, maturing temperature be 400 DEG C~700 DEG C.
In step 5), during kneading extruded moulding, those skilled in the art can add some common molecular sieves at
Type auxiliary agent promotes its molding.Preferably, sesbania powder and aqueous solution of nitric acid are added during kneading extruded moulding.It is highly preferred that
The additional amount of sesbania powder be lanthanum-phosphorus modified molecular sieves and binder gross mass 5wt%~10wt%, preferably 7wt%~
9wt%.Preferably, the concentration of the aqueous solution of nitric acid is 1wt%~10wt%.Preferably, the addition of the aqueous solution of nitric acid
Amount is 50wt%~70wt% of lanthanum-phosphorus modified molecular sieves and binder gross mass.
It is mixed in methanol and the production of benzene vapor phase alkylation that third aspect present invention also discloses catalyst as described above
Close the purposes in aromatic hydrocarbons.
Fourth aspect present invention also discloses a kind of production method of BTX aromatics, using fixed bed reactors, with methanol
It is reaction raw materials with benzene, is alkylated reaction under the catalysis of the catalyst and generates BTX aromatics.
Preferably, the reaction temperature of alkylated reaction is 250 DEG C~550 DEG C.It is highly preferred that the reaction temperature of alkylated reaction
Degree is 400 DEG C~500 DEG C.
Preferably, the reaction pressure of alkylated reaction is 0.01MPa~2.00MPa.It is highly preferred that alkylated reaction is anti-
Answering pressure is 0.1MPa~1.5MPa.
Preferably, 0.01~5.0h of methanol weight air speed-1.It is highly preferred that 0.5~2.0h of methanol weight air speed-1。
Preferably, the molar ratio of benzene and methanol is (1~30): 1.It is highly preferred that the molar ratio of benzene and methanol be (6~
18): 1
Preferably, water is additionally used in alkylated reaction, the molal quantity of water is no more than 16 times of benzene and methanol total mole number.
In the application, since benzene alkylation belongs to strong exothermal reaction, water is added during the reaction and is used as shifting thermit powder,
The heat that reaction generates can be not only removed rapidly, and maintaining reaction temperature is constant, and the addition of water can also disappear during the reaction
Carbon remover improves the anti-carbon performance of catalyst, meanwhile, water will be at war with absorption with methanol in the catalyst, reduce methanol
The occurrence probability that the side reactions such as MTO, MTG occur, improves the alkylation efficiency of methanol.
In the application, water can not also be added during the reaction, only with the charging of the mixture of methanol and benzene.Anhydrous anti-
Under the conditions of answering, carbon deposition rate can be accelerated, meanwhile, lack the competitive Adsorption of water, the probability that the side reactions such as MTO, MTG occur for methanol mentions
The alkylation efficiency of height, methanol can reduce, but in anhydrous conditions, system energy consumption also accordingly reduces, and economy is more preferable.
According to the present invention, there are water and anhydrous reaction condition, methanol can be carried out with benzene vapor phase alkylation, because
This, reacting raw materials used methanol may be selected anhydrous methanol and aqueous methanol, reduces the requirement to reaction raw materials, can further mention
High economy.But be still in actual application in strict accordance with water/(benzene+methanol) molar ratio be 0~16 charge proportion into
Row control.
Compared with prior art, in the present invention, the small and uniform nano-ZSM-5 molecular sieve by using crystal grain is stringent to control
Assistant types, order of addition and additive amount processed, while binder is added and forms to form catalyst, and in the application process of catalyst
Middle strict control reaction condition, especially water/(benzene+methanol) charge proportion, come realize improve methanol alkylation efficiency and
The purpose of catalyst anti-carbon performance；The catalyst is applied to have alkyl in methanol and benzene vapor-phase alkylation production BTX aromatics
Change high-efficient, the good feature of anti-carbon performance.
Detailed description of the invention
Fig. 1 is shown as the XRD spectra of synthesis of molecular sieve in the embodiment of the present invention 1.
Fig. 2 is shown as the SEM figure of synthesis of molecular sieve in the embodiment of the present invention 1.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than limiting the scope of protection of the present invention.The test method of actual conditions is not specified in the following example,
Usually according to normal condition, or according to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
In embodiment, the methanol conversion, toluene+dimethylbenzene selective, methanol alkylation efficiency and the carbon deposition rate that are related to
It is calculated as follows formula.
The conversion ratio (mol.%) of methanol=(molal quantity of methanol/charging methanol total mole number in 1- product) *
100%；
Toluene+dimethylbenzene selectivity (mol.%)=[fragrant in the molal quantity/product of (toluene+dimethylbenzene) in 1- product
The total mole number of hydrocarbon] * 100%；
Methanol alkylation efficiency (%)=total mole number of methanol needed for being converted to the alkyl in product aromatics/is converted to institute
The total mole number * 100% of methanol needed for having product；
Carbon deposition rate (mg/min)=post catalyst reaction carbon distribution weight (mg)/reaction time (min)
According to the present invention, above-mentioned nano-ZSM-5 molecular sieve can be synthesized according to following scheme:
1) Molecular sieve raw material molar ratio SiO2:Al2O3: template: Na2O:H2O is 1:(0.002~0.040): (0.050~
0.600): (0.030~0.150): (7~20)；
2) stainless steel crystallizing kettle is added in portions of de-ionized water in silicon source, sodium source and formula and stirred evenly, is then added
Template stirs evenly, and seals crystallizing kettle after being eventually adding silica gel particle, after stirring 20~50h of crystallization at 100~120 DEG C,
Crystallizing kettle is added in remaining deionized water in being formulated, and crystallization temperature is risen to 150~180 DEG C of continuation 10~30h of crystallization, produces
Object is washed, dry, roasting, after ion exchange, obtains H-ZSM-5 molecular sieve of the crystal grain between 50~300nm.
It can be obtained that yield stable, crystal grain is small and uniform nano-ZSM-5 molecular sieve according to above-mentioned synthetic schemes, be conducive to mention
The preparation stability of high catalyst, and then obtain the stable catalyst of reactivity worth.
Embodiment 1
(1) synthesis of HZSM-5 molecular sieve:
Raw material proportioning is SiO2:Al2O3: n-butylamine: Na2O:H2O=1:0.005:0.360:0.120:15.Match according to raw material
Than stainless steel crystallizing kettle is added in 5.50g sodium metaaluminate, 40.38g sodium hydroxide and 472.25g deionized water and is stirred evenly,
Then 117.77g n-butylamine is added to stir evenly, crystallizing kettle is sealed after being eventually adding 280.05g silica gel particle, in 110 DEG C of conditions
After lower stirring crystallization 50h, crystallizing kettle is added by metering pump in remaining 708.37g deionized water, later by crystallization temperature liter
To 170 DEG C of continuation crystallization 15h, product is washed, dry, roasting, ion exchange obtain grain size in 150 rans
HZSM-5 molecular sieve.
(2) modification of HZSM-5 molecular sieve:
The above-mentioned nano-HZSM-5 zeolite of 100g is taken, the phosphate aqueous solution for being 0.30mol/L with 250.0mL concentration is in 60 DEG C
Under be stirred to react 4 hours, the moisture in 60 DEG C of negative pressure elimination reaction liquid, 550 DEG C roast 4 hours, be made P/HZSM-5 molecular sieve,
Wherein with P2O5Meter phosphorus content is 5.0wt%.
The above-mentioned P/HZSM-5 molecular sieve of 100g is taken, the lanthanum nitrate aqueous solution for being 0.10mol/L with 190.3mL concentration is in 60 DEG C
Under be stirred to react 4 hours, the moisture in 60 DEG C of negative pressure elimination reaction liquid, 550 DEG C roast 4 hours, be made La-P/HZSM-5 molecule
Sieve, wherein with La2O3Meter lanthanum content is 3.0wt%.
(3) catalyst is prepared
100gLa-P/HZSM-5 molecular sieve molecular sieve and aluminium oxide is taken to be sufficiently mixed according to mass ratio 70:30.It is added appropriate
Sesbania powder, and the diluted nitric acid aqueous solution for accounting for that the concentration of powder gross mass 60% is 3.0wt% is added, abundant kneading extrusion obtains
The cylinder profile bar for being 1.5mm to diameter, prior to 40 DEG C at dry 6 hours, it is 6 hours dry at 120 DEG C, under air atmosphere,
550 DEG C roast 4 hours, obtain finished catalyst.
(4) evaluating catalyst
On fixed-bed reactor, methanol and benzene vapor phase alkylation preparing methylbenzene are carried out, evaluates reactivity of catalyst
Energy.Reaction condition: 460 DEG C of reaction temperature, reaction pressure 0.5MPa, benzene/methanol 8 (moles/mole), water/(benzene+methanol) mole
Than 4, methanol weight air speed 0.5h-1, reaction result is shown in Table 1.
Embodiment 2~9
Catalyst is prepared according to the method for embodiment 1 and is evaluated, the silica alumina ratio of molecular sieve is only changed, and crystallite dimension is urged
Agent P2O5And La2O3Content.Actual conditions are shown in Table 1.
Embodiment 10
Catalyst is prepared according to the method for embodiment 1 and is evaluated, and only water/(benzene+methanol) molar ratio is in reaction condition
0.Actual conditions are shown in Table 1.
Comparative example 1
Catalyst is prepared according to the method for embodiment 1 and is evaluated, only catalyst P2O5And La2O3Content be all 0.Tool
Concrete conditions in the establishment of a specific crime is shown in Table 1.
Comparative example 2
Catalyst is prepared according to the method for embodiment 1 and is evaluated, only catalyst P2O5Content be 0.Actual conditions are shown in Table
1。
Comparative example 3
Catalyst is prepared according to the method for embodiment 1 and is evaluated, only catalyst La2O3Content be 0.Actual conditions are shown in
Table 1.
Table 1
From the point of view of reaction result through the foregoing embodiment, benzene is carried out using the solution of the present invention and is reacted with methanol alkylation,
Toluene+dimethylbenzene selective > 96.5%, methanol alkylation efficiency > 96.7%, carbon deposition rate is substantially reduced, and is further illustrated
Advance of the invention.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (18)
1. a kind of alkylation catalyst, which is characterized in that the catalyst is to prepare with the following method: by nanometer ZSM-
5 molecular sieve powders are modified, mediate extruded moulding with binder, then dry and roasting；
Wherein, modified nano-ZSM-5 molecular sieve powder content is 10wt%~50wt%, and the content of binder is 50wt%
~90wt%；
It include the P of 1.0wt%~8.0wt% in modified nano-ZSM-5 molecular sieve powder2O5With 1.0wt%~5.0wt%
La2O3, remaining is nano-ZSM-5 molecular sieve.
2. alkylation catalyst according to claim 1, which is characterized in that the crystal grain diameter of nano-ZSM-5 molecular sieve is
5nm~350nm.
3. alkylation catalyst according to claim 1, which is characterized in that SiO in nano-ZSM-5 molecular sieve2With Al2O3
Molar ratio be 50~500, wherein SiO2Molal quantity be by nano-ZSM-5 molecular sieve Si element molal quantity conversion obtain
, Al2O3Molal quantity be by nano-ZSM-5 molecular sieve Al element molal quantity conversion obtain.
4. alkylation catalyst according to claim 1, which is characterized in that P in catalyst2O5Presoma be selected from phosphoric acid
One or both of with ammonium dihydrogen phosphate.
5. alkylation catalyst according to claim 1, which is characterized in that La in catalyst2O3Presoma be nitric acid
Lanthanum.
6. alkylation catalyst according to claim 1, which is characterized in that the binder is selected from aluminium oxide, Aluminum sol
With one of aluminum phosphate or a variety of.
7. a kind of method for preparing the alkylation catalyst as described in any one of claim 1~6, includes the following steps:
1) it disperses nano-ZSM-5 molecular sieve in the aqueous solution of phosphorus-containing compound and is stirred to react, remove dereaction after reaction
Moisture in liquid obtains phosphorous white powder；
2) it roasts the phosphorous white powder to obtain phosphorus modified molecular sieves；
3) it disperses the phosphorus modified molecular sieves in the aqueous solution containing lanthanum compound and is stirred to react, remove dereaction after reaction
Moisture in liquid obtains white powder containing lanthanum；
4) white powder containing lanthanum is roasted to obtain lanthanum-phosphorus modified molecular sieves；
5) lanthanum-phosphorus modified molecular sieves are uniformly mixed with binder, after kneading extruded moulding, are obtained alkylation through drying, roasting and are urged
Agent.
8. the method according to the description of claim 7 is characterized in that the concentration of the aqueous solution of phosphorus-containing compound is 0.10mol/L
~0.50mol/L.
9. the method according to the description of claim 7 is characterized in that the concentration of the aqueous solution containing lanthanum compound is 0.05mol/L
~0.30mol/L.
10. the method according to the description of claim 7 is characterized in that reaction temperature is no more than 80 DEG C in step 1).
11. the method according to the description of claim 7 is characterized in that step 2) and/or 4) in, maturing temperature be 400 DEG C~
700℃。
12. a kind of alkylation catalyst as described in any one of claims 1 to 6 is produced in methanol and benzene vapor phase alkylation
Purposes in BTX aromatics.
13. a kind of production method of BTX aromatics, which is characterized in that use fixed bed reactors, be that reaction is former with methanol and benzene
Material is alkylated reaction under the catalyst effect as described in any one of claim 1~6 and generates BTX aromatics.
14. production method according to claim 13, which is characterized in that the reaction temperature of alkylated reaction be 250 DEG C~
550℃。
15. production method according to claim 13, which is characterized in that the reaction pressure of alkylated reaction is 0.01MPa
~2.00MPa.
16. production method according to claim 13, which is characterized in that 0.01~5.0h of methanol weight air speed-1。
17. production method according to claim 13, which is characterized in that the molar ratio of benzene and methanol is (1~30): 1.
18. production method according to claim 13, which is characterized in that additionally use water in alkylated reaction, water rubs
Your number is no more than 16 times of benzene and methanol total mole number.
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