CN103418426B - Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof - Google Patents

Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof Download PDF

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CN103418426B
CN103418426B CN201210150288.1A CN201210150288A CN103418426B CN 103418426 B CN103418426 B CN 103418426B CN 201210150288 A CN201210150288 A CN 201210150288A CN 103418426 B CN103418426 B CN 103418426B
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binder
aromatichydrocarbon
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CN103418426A (en
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陈希强
汪哲明
肖景娴
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

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Abstract

The present invention relates to a kind of Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof, mainly solve the problem that during methyl alcohol aromatic hydrocarbons, reactivity is low, BTX (benzene,toluene,xylene) yield is low.The present invention is by including in terms of parts by weight: a) 70～95 parts are selected from binderless ZSM-5 5 zeolite；Thereon with being loaded in: b) 1～30 part of at least one oxide in Ag, Zn or Ga；C) technical scheme of 0～5 part of at least one oxide composition catalyst in Mo, Cu, La, P or Ce, preferably solves this problem, can be used in the industrial production of methyl alcohol aromatic hydrocarbons.

Description

Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof
Technical field
The present invention relates to a kind of methyl alcohol arenes catalytic agent and preparation method thereof, especially with regard to a kind of binder free methyl alcohol Arenes catalytic agent processed and preparation method thereof.
Background technology
Aromatic hydrocarbons, particularly light aromatics BTX (benzene,toluene,xylene) is important basic organic chemical industry's material, its yield With scale inferior to ethene and propylene, its derivative is widely used in the chemical products such as chemical fibre, plastics and rubber and becomes more meticulous In the production of product.In recent years, along with petrochemical industry and the development of textile industry, the demand of aromatic hydrocarbons constantly increases.When The main source of front BTX is catalytic reforming and drippolene by-product, and both of which is using oil as initial raw materials for production.According to Statistics, China accounts for more than the 85% of aromatic hydrocarbons total output, the aromatic hydrocarbons abroad produced for raw material with oil with the aromatic hydrocarbons that petroleum path produces Account for more than the 98% of its total output especially.Along with constantly consuming of world's crude oil and rising steadily of international oil price, aromatic hydrocarbons production capacity is subject to To suppression, production cost is unprecedented soaring.In China, current oil production rate cannot meet the demand of economic development, externally Crude oil interdependency alreadys more than 50%, adds up the first half of the year in 2011 according to Ministry of Industry and Information, and the crude oil external dependence degree of China has reached The new peak of 55.3%.To this end, find a kind of new technology that petrochemical industry can be replaced to produce aromatic hydrocarbons, China's chemical enterprise is improved Economic benefit and the energy security ensureing country have important strategic importance.
And methyl alcohol is exactly an aromatics production route the most promising by aromatisation production aromatic hydrocarbons.This on the one hand be because of For coal resources in China rich reserves, the most highly developed with the technology that coal produces methyl alcohol for raw material, thus the yield of methyl alcohol The demand producing aromatic hydrocarbons is readily satisfied with price；On the other hand, methyl alcohol problem of excess production capacity is more serious, develops methyl alcohol aromatic hydrocarbons skill Art is then conducive to alleviating this problem, effectively extends Chemical Industry chain, improves the utilization ratio of coal resources.
Common methyl alcohol arenes catalytic agent is all that to use ZSM-5 molecular sieve be acid carrier, and uses binding agent to be molded, Then load a certain amount of dehydrogenation metal component to prepare.
Chinese patent CN1880288A describes technique and the catalyst of a kind of methanol conversion for preparing arene, and this technique is with little crystalline substance Grain ZSM-5 zeolite is carrier, uses after mixing with binding agent (boehmite, gama-alumina or diatomite) extruded, Back loading active component gallium and lanthanum are prepared as catalyst, operation pressure 0.1～5.0 MPa, operation temperature 300～460 C, Raw material liq air speed is 0.1～6.0 h-1Under the conditions of, product is through refrigerated separation, and liquid phase selective is more than 33%, in liquid phase The yield of aromatic hydrocarbons is more than 60%.
CN 101244969A reports the device and method of a kind of continuous aromatization and catalyst regeneration.Including C1-C2 hydrocarbon The fluidized bed plant that class or aromatization of methanol and catalyst regenerate, and it is suitable for aromatized catalyst and the behaviour of fluidized bed process Make method.Its catalyst used is also made up of three parts, is molecular sieve, metal and structural stabilizing agent or reinforcing agent respectively (being i.e. equivalent to binding agent).Wherein molecular sieve accounts for the 50%～70% of catalyst weight, and metal accounts for 1%～10%, and remaining is then for bonding Agent.At reaction temperature 350～380 C, aromatics yield is more than 70%, and BTX is selectively more than 55%.
In sum, for commercial Application catalyst, it is typically necessary, through forming technique, catalyst is made certain shape Shape, thus obtain certain mechanical strength.Such as fixed bed used catalyst, frequently with the mode of extrusion make cylindric, three Leaf grass-like or some other special-shaped catalyst；Fluid catalyst then needs to add binding agent spray shaping.But whether Which kind of shape catalyst is, is required for reaching a common standard, i.e. catalyst and has certain mechanical strength, typically comes Saying, the crushing strength of industrial fixed bde catalyst used will be at more than 30N/cm.For molecular sieve, unprocessed is powder before Last current state, entirely without mechanical strength, is not suitable for commercial Application.And catalyst mechanical strength to be obtained can have following two side Method: one is compression molding；Two is binding agent shaping.Owing to the amount of industrial used catalyst is relatively big, use pressed-disc technique obvious Inapplicable, the technology therefore adding binding agent shaping becomes the shaping of catalyst method commonly used at present.
But add binding agent and can produce new problem, that is, binding agent can cover the part active surface of molecular sieve Long-pending, thus reduce reactant and product diffusion on a catalyst.Use the binder free catalyst then can be with Time solve molecular sieve and do not have mechanical strength and binding agent to introduce to cause the problem that catalyst effective surface reduces and diffusion limits.
So-called binder free catalyst refers generally to do not have binding agent or binder content urging less than 5% in catalyst Agent.A dragon outstanding person is dried, in organic amine with silica containing binding agent mixed-forming by ZSM-5 type hydrophobic silicalite powder Or in organic quaternary ammonium aqueous alkali or steam, prepare a kind of adhesiveless ZSM-5 type hydrophobic silicalite through Crystallizing treatment, roasting [dragon outstanding person's one hydrophobic silicon zeolite adsorbent without cohesive agent and preparation ZL 94112035.X thereof].Teng Jiawei et al. [CN 100408476C] the binding agent silica that content is 5～50 weight % is formed mixture with ZSM type molecular screen primary powder, containing In halogenation organic amine and the aqueous solution of alkyl diamine or steam, hydrothermal treatment is converted into integration ZSM type molecular sieve, i.e. without gluing Knot agent molecule sieve.Wang Deju et al. [CN 1915820A] then uses diatomite or white carbon to be primary raw material, adds crystal seed and guides Agent, and using Ludox or sodium metasilicate as binding agent, then with organic amine and steam gas-solid phase processor, it is converted into integration little Grain ZSM-5 molecular sieve.
Summary of the invention
One of the technical problem to be solved is that reactivity is low, BTX yield is low during methyl alcohol aromatic hydrocarbons Problem, it is provided that Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst.This catalyst has the advantage that reactivity is high, BTX yield is high. The two of the technical problem to be solved are to provide a kind of binder free methyl alcohol corresponding with solving one of technical problem The preparation method of arenes catalytic agent processed.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of binder free methyl alcohol system virtue Hydrocarbon catalyst, includes following components in terms of parts by weight:
A) 70～95 parts are selected from adhesiveless ZSM-5 zeolite；Thereon with being loaded in
B) 1～30 part of at least one oxide in Ag, Zn or Ga；
C) 0～5 part of at least one oxide in Mo, Cu, La, P or Ce；
Wherein, the specific surface of adhesiveless ZSM-5 zeolite is 420～560 m2/ g, the radial direction crushing strength of catalyst is big In 40N/cm.
In technique scheme, the radial direction crushing strength preferred version of catalyst is more than 60N/cm.Described binder free The preferred scope of Si/Al atomic ratio of ZSM-5 zeolite is 10～100.
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of binder free methyl alcohol system virtue The preparation method of hydrocarbon catalyst, comprises the following steps:
1) take the desired amount of template I, acid catalyst, silicon source, aluminium source and water to mix at 0～60 DEG C and obtain mixture I, hydrolyze 0.1～10h under stirring condition, then proceeded to closed container, under the conditions of 30～90 DEG C, reaction generates gel, solidifying Being drawn off after glue is aging, through being dried to obtain sample A, wherein template I is selected from polyethylene glycol, PEO, polyoxy second At least one in alkene-polyoxypropylene polyoxyethylene (P123) or cetyl trimethylammonium bromide (CTAB)；Acid catalyst selects At least one in hydrochloric acid, nitric acid or sulfuric acid；Silicon source is selected from methyl silicate (TMOS), tetraethyl orthosilicate (TEOS) or positive silicon At least one in propyl propionate (TPOS)；At least one in aluminum nitrate, aluminium chloride or aluminum sulfate of aluminium source；In mixture I The mass ratio of each species is: template: SiO2=0.5～1.8:1, H+: SiO2=0.005～0.02:1, Al2O3:SiO2=0.005 ～0.05:1, H2O:SiO2=5～8:1；
2) sample A is obtained mixture II with crystal seed, binding agent mixing aftershaping, and is dried to obtain sample B, wherein crystal seed Selected from HZSM-5 molecular sieve, the Si/Al atomic ratio of molecular sieve is 10～100；Binding agent is white selected from Ludox, Alumina gel, gas phase At least one in carbon black, liquid phase white carbon or boehmite, in mixture II, the mass ratio of each species is: crystal seed: sample A =0.001～0.1:1, binding agent: sample A=0.1～2:1；
3) sample B is placed in the upper strata of crystallization still, and template II and water are placed by lower floor, 100～180 DEG C of spontaneous pressures Crystallization 0.5d～4 days under the conditions of power, product through washing, be dried and roasting remove template after obtain sample C, wherein, template The agent II one in TPAOH, ethylenediamine, triethylamine, n-propylamine, n-butylamine or hexamethylene diamine, the matter of each species Amount ratio is: template II: sample B=0.001～4:1, water: sample B=1～100:1；
4) after loading the oxide of the desired amount of modification element M and N on sample C, through 60～130 DEG C of dry 2- 24h, 450～650 DEG C of roastings 1～8h prepare Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst, wherein, modify element M selected from Ag, Zn or At least one in Ga, at least one in Mo, Cu, La, P or Ce of N.
So-called binder free catalyst refers generally to do not have binding agent or binder content urging less than 5% in catalyst Agent.The present invention has the sieve and silica-sesquioxide presoma of relatively Large ratio surface by first preparing, and then uses forming technique system For obtaining catalyst precursor, and use gas phase crystallization technology to be translated into ZSM-5 zeolite, thus obtain relatively Large ratio surface Adhesiveless ZSM-5 catalyst carrier.Finally by load active component on this carrier, thus prepare all-in-one-piece nothing Binder-type methyl alcohol arenes catalytic agent.Amorphous silicon aluminium species used by shaping of catalyst has bigger specific surface, Thus the catalyst precursor of shaping has had bigger specific surface, add gas phase crystallization and define a large amount of ZSM-5 boiling Micropore specific surface contained by stone so that whole catalyst has the biggest specific surface, beneficially reactant and product in catalysis Diffusion in agent, improves the reactivity of catalyst.At reaction temperature 430 DEG C, normal pressure, mass space velocity=4.0h-1, normal pressure Under reaction condition, with methyl alcohol as reaction raw materials, the catalyst of the present invention modifies element with identical silica alumina ratio and load same amount Binder-type catalyst compare, aromatics yield and BTX yield improve more than 8%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.But the present invention is not limited in these embodiments.
Detailed description of the invention
[embodiment 1]
1) weigh 2.8g polyethylene glycol, 4.0g P123,16g concentration is the salpeter solution of 1mol/L, 3.9g aluminum nitrate, 27.9g tetraethyl orthosilicate and the mixing of 28g aqueous phase, be uniformly dissolved under agitation, and continues to hydrolyze 2h.Proceeded to close subsequently Close container, under the conditions of 65 DEG C, make its gel aging 24h, take out gel subsequently, through being dried to obtain sample A1.
2) 7.0g sample A1,0.3g HZSM-5 (SiO is weighed2/Al2O3Ratio=25) molecular sieve, 7.2g Ludox (SiO2Matter Amount concentration 40%), 0.17g boehmite, 0.3g sesbania powder and 3.9g dilute hydrochloric acid solution (concentration is 1mol/L), mediate uniformly The mode of rear employing extrusion makes cylindrical pellet, through being dried to obtain sample B1.
3) taking 1.5g sample B1 and be placed in the upper strata of crystallization still, 4.0g water and 1.0g TPAOH place in lower floor, spontaneous In 160 DEG C of crystallization 2d under pressure condition, take out sample subsequently, through washing, be dried and obtain sample after roasting removing template C1。
4) taking 1.0g sample C1,0.3g zinc nitrate, 0.5g aqueous phase mixes, and uses Rotary Evaporators to be evaporated excessive moisture, Sample prepares methyl alcohol arenes catalytic agent MTA-1, wherein with mass fraction through 120 DEG C of dry 12h, 550 DEG C of roasting 5h subsequently Meter, the content of Zn oxide is 7 parts.
[embodiment 2～6]
Weigh the sample C1 that embodiment 1 prepares, adjust the amount of zinc nitrate, be prepared as respectively Zn oxide content be 1.2 parts, 2.4 parts, 3.6 parts, 14.5 parts, the catalyst of 20 parts, be denoted as MTA-2, MTA-3, MTA-4, MTA-5, MTA-6.
[embodiment 7]
1) 10.0g sample A1,0.1g HZSM-5 (SiO is weighed2/Al2O3Ratio=38) molecular sieve, 2g gas-phase silica, 9g Alumina gel (Al2O3Mass concentration 21%), 0.2g soluble starch, mediate uniform aftershaping, obtaining sample B2 through being dried.
2) taking 5g sample B2 and be placed in the upper strata of crystallization still, 10g water, 1g NaOH, 4g triethylamine are placed by lower floor, certainly In 180 DEG C of crystallization 20h under raw pressure condition, product is through washing, be dried and obtaining sample C2 after roasting removing template.
3) using silver nitrate solution is maceration extract carried metal Ag on sample C2.Sample through 100 DEG C of dry 20h, 480 DEG C roasting 5h prepares methyl alcohol arenes catalytic agent MTA-7, and wherein in terms of mass fraction, the content of Ag oxide is 1.1 parts.
[embodiment 8]
1) 8.0g sample A1,0.8g HZSM-5 (SiO is weighed2/Al2O3Ratio=200) molecular sieve, 2g liquid phase white carbon, 4g Boehmite, 14g dust technology (mass concentration is 1.5%), 0.3g methylcellulose, mediate uniform aftershaping, through being dried Obtain sample B3
2) taking 3g sample B3 and be placed in the upper strata of crystallization still, 5g water, 0.8g NaOH, 3g hexamethylene diamine are placed by lower floor, certainly In 140 DEG C of crystallization 72h under raw pressure condition, product is through washing, be dried and obtaining sample C3 after roasting removing template.
3) using gallium nitrate solution is maceration extract carried metal Ga on sample C3.Sample through 110 DEG C of dry 18h, 550 Roasting 4h prepares methyl alcohol arenes catalytic agent MTA-8, and wherein in terms of mass fraction, the content of Ga oxide is 2.7 parts.
[embodiment 9]
1) weigh 15.6g PEO, 12g P123,117g concentration is the hydrochloric acid solution of 1mol/L, 5.2g aluminum sulfate, 52.9g methyl silicate and the mixing of 110g aqueous phase, be uniformly dissolved under agitation, and ultrasonic hydrolysis 10 minutes.Subsequently by it Proceed to closed container, the aging 36h of gel under the conditions of 60 DEG C, takes out gel, subsequently through being dried to obtain sample A2.
2) 20g sample A2,2g HZSM-5 (SiO is weighed2/Al2O3Ratio=50) molecular sieve, 6g gas-phase silica, 1g intend thin water Aluminium stone, 5.5g Ludox (SiO2Mass content 40%), 16g concentration be the dilute nitric acid solution of 1.5%, use extrusion after mediating uniformly Mode be molded, through being dried to obtain sample B4.
3) taking 5.0g sample B4, the upper strata being placed on crystallization still of absorption 1.0g TPAOH, 10g water is placed by lower floor, With 170 DEG C of crystallization 48h under the conditions of self-generated pressure, product is through washing, be dried and obtaining sample C4 after roasting removing template.
4) take 5.0g sample C4, join 1.37g zinc nitrate and in the middle of solution that 3.5g water is made into, after mixing through 130 DEG C of dry 8h, 600 DEG C of roasting 3h prepare methyl alcohol arenes catalytic agent MTA-9, wherein in terms of mass fraction, Zn oxide Content is 7 parts.
[embodiment 10～14]
The catalyst MTA-9 of Example 9 preparation, prepares first after the oxide of Mo, Cu, La, P and Ce of load 2% respectively Alcohol arenes catalytic agent MTA-10, MTA-11, MTA-12, MTA-13, MTA-14.
[embodiment 15]
1) 4g P123,35g positive silicic acid propyl ester, 0.84g AlCl are weighed3 .6H2O, 24g concentration be 1mol/L sulfuric acid and 25g aqueous phase mixes, and is uniformly dissolved under the conditions of ice-water bath, and stirs hydrolysis 6h.Proceeded to closed container subsequently, under the conditions of 80 DEG C Make its gel aging 8h, through being dried to obtain sample A3 after taking-up.
2) 10.0g sample A3,0.4g HZSM-5 (SiO is weighed2/Al2O3Ratio=100) molecular sieve, 1.0g boehmite, 8g Ludox, 4g dust technology (1mol/L), 0.2g soluble starch, mediate uniform aftershaping, through being dried to obtain sample B5
3) taking 5g sample B5 and be placed in the upper strata of crystallization still, 5g water, 0.8g NaOH, 3g n-butylamine are placed by lower floor, certainly In 120 DEG C of crystallization 96h under raw pressure condition, product is through washing, be dried and obtaining sample C5 after roasting removing template.
4) using zinc nitrate solution is maceration extract carried metal Zn on sample C5.Sample through 80 DEG C of dry 20h, 500 DEG C roasting 6h prepares methyl alcohol arenes catalytic agent MTA-15, and wherein in terms of mass fraction, the content of Zn oxide is 3.6 parts.
[embodiment 16]
1) weigh 2g CTAB, 2g P123,19.5g methyl silicate, 0.48g aluminum nitrate, 16g concentration are the salt of 1mol/L Acid solution and the mixing of 18g aqueous phase, dissolve under stirring at normal temperature, and continue to hydrolyze after 4h and proceed to closed container, makes it under the conditions of 70 DEG C Gel aging 24h, through being dried to obtain sample A4 after taking-up.
2) 10g sample A4,1.0g HZSM-5 (SiO is taken2/Al2O3Ratio=200) molecular sieve, 10g Ludox (SiO2 content 40%), 0.3g sesbania powder, mediate uniform aftershaping, through being dried to obtain sample B6.
3) taking 3g sample B6 and be placed in the upper strata of crystallization still, 6.0g water and 1.5g TPAOH place in lower floor, in spontaneous pressure With 150 DEG C of crystallization 2.5d under the conditions of power, take out sample subsequently, through washing, be dried and obtain sample after roasting removing template C6。
4) taking sample C6, using gallium nitrate solution is that maceration extract is at supported on carriers metal Ga.Sample is dried through 60 DEG C 24h, 600 DEG C of roasting 2h prepare methyl alcohol arenes catalytic agent MTA-16, and wherein in terms of mass fraction, the content of Ga oxide is 3.6 part.
[comparative example 1]
Contrast with embodiment 1
1) 10g HZSM-5 (SiO is weighed2/Al2O3Ratio=25) molecular sieve, 3.5g boehmite, 0.2g sesbania powder, 10g Dilute nitric acid solution (mass concentration 1.5%), mediates uniform aftershaping, and through being dried, roasting obtains sample B7.
2) taking B7, using zinc nitrate solution is that maceration extract loads Zn on B7, through 120 DEG C of dry 12h, 550 DEG C of roastings 5h prepares methyl alcohol arenes catalytic agent MTA-17, and wherein in terms of mass fraction, the content of Zn oxide is 7 parts.
[comparative example 2]
Contrast with embodiment 13, use the method for comparative example 1 to prepare methyl alcohol arenes catalytic agent MTA-18, wherein The SiO of HZSM-52/Al2O3Ratio=50, consumption of binder 30%, modifying element is Zn and P, and the content of its oxide is respectively catalysis The 7% and 2% of agent weight.
The materialization of each catalyst characterizes and at reaction temperature 430 DEG C, normal pressure, mass space velocity=4.0h-1, the reaction of normal pressure Under the conditions of, the aromatization result with methyl alcohol as reaction raw materials is listed in table 1.
The composition of each catalyst of table 1 and catalytic performance

Claims (3)

1. a Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst, includes following components in terms of parts by weight:
A) 70～95 parts are selected from adhesiveless ZSM-5 zeolite；Thereon with being loaded in
B) 1～30 part of at least one oxide in Ag, Zn or Ga；
C) 0～5 part of at least one oxide in Mo, Cu, La, P or Ce；
Wherein, the specific surface of adhesiveless ZSM-5 zeolite is 420～560m2/ g, the radial direction crushing strength of catalyst is more than 40N/ cm；
Described method for preparing catalyst comprises the following steps:
1) take the desired amount of template I, acid catalyst, silicon source, aluminium source and water to mix at 0～60 DEG C and obtain mixture I, stir Hydrolyzing 0.1～10h under the conditions of mixing, then proceeded to closed container, under the conditions of 30～90 DEG C, reaction generates gel, and gel is old Being drawn off after change, through being dried to obtain sample A, wherein template I is selected from polyethylene glycol, PEO, polyoxyethylene-poly- At least one in oxypropylene-polyoxyethylene (P123) or cetyl trimethylammonium bromide (CTAB)；Acid catalyst is selected from salt At least one in acid, nitric acid or sulfuric acid；Silicon source is selected from methyl silicate (TMOS), tetraethyl orthosilicate (TEOS) or positive silicic acid third At least one in ester (TPOS)；At least one in aluminum nitrate, aluminium chloride or aluminum sulfate of aluminium source；Each thing in mixture I The mass ratio planted is: template: SiO2=0.5～1.8:1, H+:SiO2=0.005～0.02:1, Al2O3:SiO2=0.005～ 0.05:1, H2O:SiO2=5～8:1；
2) being obtained mixture II with crystal seed, binding agent mixing aftershaping, and be dried to obtain sample B by sample A, wherein crystal seed is selected from HZSM-5 molecular sieve, the Si/Al atomic ratio of molecular sieve is 10～100；Binding agent selected from Ludox, Alumina gel, gas-phase silica, At least one in liquid phase white carbon or boehmite, in mixture II, the mass ratio of each species is: crystal seed: sample A= 0.001～0.1:1, binding agent: sample A=0.1～2:1；
3) sample B is placed in the upper strata of crystallization still, and template II and water are placed by lower floor, at 100～180 DEG C of self-generated pressure bars Crystallization 0.5d～4 days under part, product through washing, be dried and roasting remove template after obtain sample C, wherein, template II One in TPAOH, ethylenediamine, triethylamine, n-propylamine, n-butylamine or hexamethylene diamine, the mass ratio of each species For: template II: sample B=0.001～4:1, water: sample B=1～100:1；
4) after loading the oxide of the desired amount of modification element M and N on sample C, through 60～130 DEG C of dry 2-24h, 450～650 DEG C of roastings 1～8h prepare Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst, wherein, modify element M in Ag, Zn or Ga At least one, at least one in Mo, Cu, La, P or Ce of N.
Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst the most according to claim 1, it is characterised in that the radial direction crushing of catalyst is strong Degree is more than 60N/cm.
Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst the most according to claim 1, it is characterised in that described adhesiveless ZSM-5 boils The Si/Al atomic ratio of stone is 10～100.
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CN103864564B (en) * 2014-02-24 2015-07-08 中国海洋石油总公司 Technique for processing methanol-to-propylene by-products
CN105498829B (en) * 2015-12-10 2018-06-26 大唐国际化工技术研究院有限公司 A kind of aromatization of methanol catalyst and its preparation method and application
CN106986735B (en) * 2017-04-18 2019-11-15 罗帮亮 A method of the methanol based on porous structure Zeolite molecular sieve catalysis prepares aromatic hydrocarbons
CN111111752B (en) * 2018-10-30 2022-09-06 中国石油化工股份有限公司 Binder-free monolithic catalyst, preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347742A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials
CN102371177A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347742A (en) * 2007-07-18 2009-01-21 中国石油化工股份有限公司 Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials
CN102371177A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof

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