CN103920525B - A kind of preparation method and application of the catalyst of dimethyl ether and benzene alkylation - Google Patents

A kind of preparation method and application of the catalyst of dimethyl ether and benzene alkylation Download PDF

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CN103920525B
CN103920525B CN201310014560.8A CN201310014560A CN103920525B CN 103920525 B CN103920525 B CN 103920525B CN 201310014560 A CN201310014560 A CN 201310014560A CN 103920525 B CN103920525 B CN 103920525B
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catalyst
dimethyl ether
molecular sieve
benzene
zsm
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CN103920525A (en
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徐龙伢
刘惠
辛文杰
刘盛林
谢素娟
李秀杰
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Dalian Institute of Chemical Physics of CAS
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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
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    • 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 preparation method and application of the catalyst of a kind of dimethyl ether and benzene alkylation, concretely comprise the following steps: the superfine rare-earth ZSM 11 molecular sieve ammonium nitrate solution exchange that will prepare, and are dried, and H type molecular sieve is made in roasting；H type molecular sieve uses zinc acetate presoma by ion exchange carried metal zinc, microwave treatment, roasting, prepares required catalyst.Catalyst prepared by the present invention is applied to dimethyl ether and benzene and is generated the C7 C9 aromatic hydrocarbons of high yield, by-product height selective olefin simultaneously by aromatization.It is an advantage of the current invention that: compared with the catalyst of unsupported metallic zinc, modified molecular sieve catalyst shows lower C10 +Ethylene in weight virtue and product, propylene and the higher feature of butylene selectivity.

Description

A kind of preparation method and application of the catalyst of dimethyl ether and benzene alkylation
Technical field
The present invention relates to the production technology of petrochemicals, be specifically related to the preparation method and application of the catalyst of a kind of dimethyl ether and benzene alkylation.
Background technology
Aromatic hydrocarbons is the important foundation raw material of petrochemical industry, and in the known organic compound of sum about 8,000,000 kinds, aromatic compound account for about 30%.Aromatic hydrocarbons is essentially from catalytic reforming, Pintsch process ethylene by-product, coal processing by-product, light hydrocarbon aromatisation, [Tao Zhihua, Huang Zhongjiu edit for Zhao Rendian, golden evident gift in conversions between aromatic hydrocarbons etc., aromatic hydrocarbons engineering, Chemical Industry Press, Beijing first impression in August calendar year 2001].The aromatic hydrocarbons purity that petroleum path obtains is high, is suitable to prepare various high-quality chemicals.The aromatic hydrocarbons that coal (dry distilling) route obtains is owing to containing thiophene-based impurity, quality is relatively low, and application is limited to, along with petroleum resources worsening shortages, the supply of aromatic hydrocarbons is in nervous trend, and price does not occupies, greatly improve the manufacturing cost of subsequent chemicals so that it is sell and be affected.And utilize natural gas (main component methane) or petroleum refinery's dry gas (mainly containing methane, ethane, ethylene) carry out anaerobic aromatization with oil liquefied gas or methanol (dimethyl ether) and prepare aromatic hydrocarbons and be all academic circles at present and industrial quarters compares popular research topic.
The raw materials such as methanol can be prepared from coal or natural gas gasifying and methanol-fueled CLC respectively, and the amount of having is big, the advantage of low cost, and its activity is of a relatively high, can be converted completely with molecular sieve composite catalyst by metal under 350-500 ° of C.Ratio methane, propane, ethane etc. is more convenient, prepares aromatic hydrocarbons efficiently.But, aromatization of methanol reaction generates substantial amounts of water during generating aromatic hydrocarbons.So, in high temperature environments, the activity of the catalyst containing molecular sieve can be had a negative impact (include affecting the absorption of other hydro carbons and cause molecular sieve dealuminzation and lose activity) by water vapour.During long reaction, the acidity of catalyst can be caused significantly to decline, and activity can not have efficient recovery, catalyst life also can be greatly shortened.
In fact, methanol dehydration generates dimethyl ether, and then aromatisation is also effectively supplementing of methanol utilization.Aromatic hydrocarbons is obtained by methanol, dimethyl ether, initially see MTG (the Methanol to Gasoline) technology of Mobil company of U.S. exploitation, 20 century 70 Mobil companies develop ZSM-5 zeolite catalyst, make methanol, dimethyl ether conversion become high-knock rating gasoline, its product composition contains the aromatic hydrocarbons of 30%.1985, Mobil company, in its United States Patent (USP) USP4590321 applied for, discloses methanol, the result of study of dimethyl ether conversion aromatic hydrocarbons first, and this research uses the phosphorous ZSM-5 molecular sieve for 2.7wt% to be catalyst, reaction temperature is 400-450 ° of C, methanol, dimethyl ether weight space velocity 1.3h-1.Result shows, the ZSM-5 catalyst modified through phosphorus the selectivity of higher hydrocarbon (C5-C9), aromatic hydrocarbons multiple indexs such as selectivity in terms of be better than the ZSM-5 molecular sieve catalyst of non-modified.But its primary product remains as the low-carbon (LC) hydro carbons of C1-C4, and total arene content is the highest.1986, Mobil company applied for United States Patent (USP) USP4686312, disclosed a kind of multistage reaction process that low-carbon oxygen-containing compound is converted into the product rich in aromatic hydrocarbons；In first paragraph reactor, methanol, dimethyl ether are first converted into based on the product of preparing low carbon hydrocarbons class, there is aromatization in these products in second stage reactor under the effect of catalyst, and obtains the product rich in aromatic hydrocarbons (benzene,toluene,xylene and heavy arene) further.2002, United States Patent (USP) USP0099249A1 of Chevron Phillips company disclosed two kinds of molecular sieve catalyst technology of Joint Production aromatic hydrocarbons by methanol, dimethyl ether of a kind of employing；Wherein the first catalyst is sial phosphorus molecular sieve, and the second catalyst is containing metallic zinc and from Group IIIA or the molecular sieve catalyst of group vib element.Using above two molecular sieve catalyst, and be combined in a certain way, this invention obtains methanol, dimethyl ether conversion preparing aromatic hydrocarbon, a kind of effective ways of particularly BTX (benzene, toluene, dimethylbenzene).
Kecskem é ti etc. [Kecskem é ti A, Barthos R, Solymosi F.J Catal, 2008,258:111] report Mo2Dimethyl ether aromatization on C/ZSM-5 catalyst, under 450 ° of C during reaction, Mo2C load capacity be 10% catalyst on total arenes selectivity be 42.5%, C8 selectivity is 22.3%.[Fang Yiwen, Song Yibing, grandson's length is brave for Sun Changyong.Catalysis journal, 2010,31 (3): 264] report H-ZSM-5 molecular sieve catalyst is acid enhancing and acid site increase beneficially dimethyl ether aromatisation.When adding 2%Zn in H-ZSM-5 catalyst, under 360 ° of C, during reaction, total arenes yield increases to 66.2% from 50.0%, and C8 aromatics yield increases to 39.0% from 28.6%.When reaction temperature is increased to 480 ° of C, total arenes yield increases to 78.0%.Its economic worth produces gasoline far above MTG method or methane aromatizing produces benzene.
Shanxi coalification patent CN1880288A in use methanol, dimethyl ether be raw material, modified ZSM-5 is catalyst, by methanol, dimethyl ether conversion be aromatic hydrocarbons be main product, gas-phase product lower carbon number hydrocarbons and liquid product are separated by cooled separation, liquid product is through extract and separate, obtain aromatic hydrocarbons and non-aromatics, the further aromatisation of low-carbon (LC) hydro carbons.But during alkane aromatization, hydrogen has a strong impact on aromatisation productivity and the selectivity of alkane, therefore the gas-phase product of methanol, dimethyl ether aromatisation is directly entered low-carbon (LC) aromatizing reaction of hydrocarbons and carries out the technique not optimum process of aromatization.
Patent CN201010111821.4 disclosure dimethyl ether aromatisation, compared with aromatization of methanol process, has the advantage that
1) dimethyl ether can be obtained sterling by aromatization of methanol dehydration preparation after being then separated from water.In aromatization reactor, the water generating every mole of aromatic hydrocarbons by-product reduces 30-50% than direct methyl ether aromatization process.This process is equivalent to portion of water be separated out in advance, thus reduces the chance of aromatized catalyst contact water, can be improved 1-3 times the catalyst life-span at high temperature.
2) dimethyl ether is first dehydrated the process of aromatisation by methanol again, first uses dehydrant, re-uses aromatized catalyst so that the consumption of aromatized catalyst reduces by 30%.Owing on catalyst in dimethyl ether aromatization process, the water of absorption reduces, acid increase, aromatics yield is than aromatization of methanol height 5-15%.Make the time of gas purging in catalyst regeneration reactor shorten simultaneously, 20 ° of C of regeneration temperature can be properly increased so that regenerated catalyst can increase by 5% for the heat that aromatization is taken back.During the reduction of water partial pressure, also make the size of aromatization reactor reduce 20%, the cost of aromatization reactor reduces.
3) dimethyl ether is gaseous state, and the dissolubility in water is less than methanol, so can reduce complexity during follow-up being separated from water.
4) using fluidized-bed reactor, feed with methanol, if degree of superheat is inadequate, partially liq can make the small particle catalyst of fluid bed easily harden or difficult fluidisation.And dimethyl ether is gaseous feed, then it is prevented effectively from this shortcoming, the operation of fluid bed can be made to become more steadily with easy.
Chinese patent CN201010111821.4 discloses continuously aromatizing dimethyl ether and catalyst regeneration method and device.This is a typical process patent, and (fixed bed carries out continuous print aromatization and catalyst regeneration in moving bed and fluid bed combination unit at certain reactor to utilize specific catalyst.Utilize this device and catalyst and method, pure Dimethyl ether can be processed or containing the mixing raw material of dimethyl ether, there is the activity of catalyst in regulation aromatization reactor, reach continuous high-efficient and convert dimethyl ether and height selectively produces the purpose of aromatic hydrocarbons.Chinese patent CN201010146915.5 discloses a kind of methanol or the system of dimethyl ether conversion preparing aromatic hydrocarbon and technique CN201010111821.4 and 201010146915.5 is typical process patent, and non-catalytic patent).First material benzenemethanol or dimethyl ether react in aromatization reactor, after reacted product is separated, and H2, methane, mixing C8 aromatic hydrocarbons and part C9+ hydro carbons is as output of products system, and C2+ non-aromatics and except mixing C8 aromatic hydrocarbons and part C9Aromatic hydrocarbons outside+hydro carbons then returns respective reaction device as circulation logistics and carries out further aromatization.Use this technique, by the product in methanol or dimethyl ether aromatization process is separated and recycles, not only improve yield and the selectivity of material aromatic hydrocarbons, and technique is flexible, target product can be converted according to the demand in market.
Chinese patent CN201110070849.2 discloses a kind of benzene and the catalyst of methanol alkylation and preparation thereof and application；Described catalyst is with H type MCM-56 zeolite and γ-or η-Al2O3For complex carrier, one or more in load molybdenum, nickel, magnesium, lanthanum, boron or its oxide are constituted, and in terms of vehicle weight 100%, in carrier, H type MCM-56 zeolite accounts for 50-80%, Al2O3Accounting for 20-50%, the molybdenum, nickel, magnesium, lanthanum, the metal of boron or its oxide that are loaded are the 3-20% of vehicle weight；This catalyst has the activity of conversion of higher benzene and methanol, and there is higher dimethylbenzene selective, the conversion ratio of benzene reaches more than 50%, and the selectivity of toluene and dimethylbenzene is more than 90%, take full advantage of benzene and methanol resource, again the relative reduction production cost of toluene and dimethylbenzene.
Chinese patent CN200910075173.9 discloses a kind of benzene and methanol alkylation preparing methylbenzene and the method for dimethylbenzene, benzene feedstock, the benzene that rectification is reclaimed feeds together with methanol, is regulated the amount of toluene and dimethylbenzene by the ratio of benzene feed and methanol, has the advantages that catalyst choice is high.The catalyst used is Beta, Y, modenite, ZSM-5 and ZSM-22, ZSM-11 molecular sieve.
Chinese patent CN201110100011.3 discloses a kind of benzene and methanol or the method for dimethyl ether dimethylbenzene.Benzene and methanol are raw material, reaction temperature 300-500 ° C, reaction pressure 0.5-3MPa, feed space velocity 0.8-3h-1Raw material contacts (containing one or more free molecular sieves, solidification mineral acid, heteropoly acid, solid super-strong acid isoreactivity component) and occurs alkylated reaction to obtain dimethylbenzene with solid acid, preferably solve petroleum resources limited, benzene and methanol production capacity surplus, benzene or can not be difficult to make the problem that dimethylbenzene, methanol or dimethyl ether are directly translated into dimethylbenzene route selection and the too low material consumption of yield, energy consumption is high.
Chinese patent CN201110100004.3 discloses a kind of benzene and methanol or the method for dimethyl ether grade oil toluene.This invention is by using the solid acid catalyst of a kind of modification, with benzene and methanol or dimethyl ether as raw material, in reaction temperature 250-600 ° C, reaction pressure 0.05-5.0MPa, raw material weight air speed 0.3-1h-1Under the conditions of, make raw material at catalyst (selected from ZSM-5, ZSM-12, modenite, USY, beta-molecular sieve, UZM molecular sieve, at least one in EU-1 molecular sieve or MCM-41 molecular sieve, at least one in the metallic element containing Mg, Ga, Ba, Zn, Ga, Mo, Ni, Co, W, Cu, Fe, Zr, Ti, Pt, Pd, Sn, Pb, La or Ce, containing at least one in P, S, Cl, B nonmetalloid) above occur alkylated reaction to obtain toluene.
[the Sz é chenyi A such as Sz é chenyi, Solymosi F.Catal Lett, 2009,127:13] report dimethyl ether and benzene coreaction under the conditions of 200-500 ° of C, reaction is carried out on modified zsm-5 zeolite pure respectively, find that temperature, at 350 ° of more than C, significantly increases toluene, dimethylbenzene and the productivity of C9 aromatic hydrocarbons after adding benzene.When with Mo2After C and ZnO decorating molecule sieve, reactivity worth gets a promotion further.
It addition, low-carbon alkene especially ethylene, propylene is important industrial chemicals.General using cracking process to produce low alkene, along with the market demand is the most powerful and oil price soaring, traditional petroleum cracking method produces low alkene cannot meet needs day by day.Under this background, each big iea and company are devoted to develop the low-carbon alkene production technology of petroleum replacing one after another.In fact, dimethyl ether and benzene react generation aromatic hydrocarbons, if higher selectivity system can be had in remaining non-aromatic product to generate, are also one of good approach obtaining alkene.By coal gasification producing synthesis gas, dimethyl ether and the benzene then produce methanol, being generated again by methanol dehydration reacts the novel process of aromatic hydrocarbons by-product height selectivity low-carbon alkene processed, is to open up a new way for the energy strategy of coal for replacing oil.
From upper analysis, dimethyl ether and benzene alkylation reaction relate to patent and article is less, relating generally to is ZSM-5 molecular sieve system, and at superfine rare-earth-ZSM-11 molecular sieve report seldom, although being ZSM Series Molecules sieve, but the former belongs to MFI topological structure (being made up of the linear type duct intersected and sinusoidal duct), and the latter is MEL topological structure (cross one another straight hole road), there are some differences in framing structure, is mainly reflected on the cross point in duct.It addition, report is conventional infusion process for this catalysts carried metal mode at present, metal precursor is nitrate or halides, almost without relating to microwave treatment.It is known that conventional preparation catalyst, especially when zinc load capacity height, metal can be uneven in molecular sieve carrier distribution, and in high-temperature roasting catalyst process, metal is easily assembled and sinters, thus affects catalyst reaction performance.The present invention uses zinc acetate to be presoma, by the way of ion exchanges, metallic zinc is distributed evenly in inside and outside the duct of molecular sieve, microwave treatment makes acetate ion decompose, metallic zinc ad-hoc location grappling in molecular sieve simultaneously, in high-temperature calcination process, metal is not easy to reunite, thus can behave as high response energy.It addition, this product should reduce C10 as far as possible+Weight virtue generates, because the active center of its easy covering catalyst, shortens catalyst service life.On the one hand the interpolation of rare earth can improve the acid distribution of ZSM-11 molecular sieve catalyst, on the other hand can improve hydro-thermal and the reaction stability of catalyst.
Summary of the invention
It is an object of the invention to provide the preparation method and application of the catalyst of a kind of dimethyl ether and benzene alkylation, by the catalyst that the present invention is modified, dimethyl ether and benzene can be converted into C7-C9 aromatic hydrocarbons simultaneously by aromatization, suppress C10+Weight virtue, by-product height selective olefin.
The invention provides a kind of preparation method reacted for dimethyl ether and benzene and generate aromatic hydrocarbons by-product olefin hydrocarbon molecules sieve catalyst, concrete grammar step is:
(1) by the superfine rare-earth-ZSM-11 molecular screen primary powder for preparing, (particle diameter is 100-1000nm, preferable particle size is 100-600nm), exchange in 70 ~ 90 ° of C with the ammonium nitrate solution of 0.5 ~ 1.0mol/L, after drying in 500 ~ 550 ° of C roasting 3 ~ 5h, make H-type molecular sieve；
(2) product obtained by (1) uses zinc acetate presoma by ion exchange carried metal zinc, the load capacity of metallic zinc is 0.5 ~ 12.0wt% (the preferably load capacity of zinc is 0.5 ~ 6.0wt%), 120-150 ° of C dries 2h, microwave treatment 0.2-1.5h (the preferred process time is 0.4 ~ 1h), 400-700 ° of C roasting 3-6h in air atmosphere, prepares required catalyst.
Putting it briefly, the catalyst that the present invention provides is to be exchanged through ammonia by superfine rare-earth-ZSM-11 molecular sieve, is dried, and is fired into H-type molecular sieve, then ion exchange carried metal zinc, and microwave treatment and roasting prepare finished catalyst.
By the catalyst that the present invention is modified, dimethyl ether and benzene can be generated the C7-C9 aromatic hydrocarbons of high yield, simultaneously by-product height selective olefin by aromatization.
Detailed description of the invention
The present invention will be further described by the following examples, but not thereby limiting the invention.
Comparative example 1
By a certain amount of particle diameter 450nm rare earth-ZSM-5 molecular sieve (content of rare earth account for rare earth-ZSM-5 molecular sieve 1.2 weight %), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, zinc acetate solution, 130 ° of C is used to dry 2h, microwave treatment 0.5h (the high-pressure sealed microwave synthesis device of MARS of U.S. CE M company, the most identical), 580 ° of C roasting 4h, catalyst Z n load capacity 4wt% of gained, it is denoted as catalyst A.
Comparative example 2
By a certain amount of particle diameter 450nm rare earth-ZSM-11 molecular sieve 1.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then infusion process zinc supported metal, use zinc acetate solution, 130 ° of C dry 2h, microwave treatment 0.5h, 580 ° of C roasting 4h, catalyst Z n load capacity 4wt% of gained, is denoted as catalyst B.
Comparative example 3
By a certain amount of particle diameter 450nm rare earth-ZSM-11 molecular sieve 1.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc nitrate solution, 130 ° of C dry 2h, microwave treatment 0.5h, 580 ° of C roasting 4h, catalyst Z n load capacity 4wt% of gained, is denoted as catalyst C.
Comparative example 4
By a certain amount of particle diameter 450nm rare earth-ZSM-11 molecular sieve (content of rare earth account for rare earth-ZSM-11 molecular sieve 1.2 weight %), exchanging 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 130 ° of C dry 2h, 580 ° of C roasting 4h, catalyst Z n load capacity 4wt% of gained, it is denoted as catalyst D.
Comparative example 5
By a certain amount of particle diameter 450nm rare earth-ZSM-11 molecular sieve (content of rare earth account for rare earth-ZSM-11 molecular sieve 1.2 weight %), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve catalyst, be denoted as catalyst E.
Embodiment 1
By a certain amount of particle diameter 450nm rare earth-ZSM-11 molecular sieve 1.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 80 ° of C, wash 2 times, 120 ° of C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 130 ° of C dry 2h, microwave treatment 0.5h, 580 ° of C roasting 4h, catalyst Z n load capacity 4wt% of gained, is denoted as catalyst F.
Embodiment 2
By a certain amount of particle diameter 150nm rare earth-ZSM-11 molecular sieve 2.5 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 75 ° of C, wash 2 times, 120 ° of C are dried, 530 ° of C roasting 4h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 140 ° of C dry 2h, microwave treatment 0.8h, 500 ° of C roasting 5h, catalyst Z n load capacity 1wt% of gained, is denoted as catalyst G.
Embodiment 3
By a certain amount of particle diameter 550nm rare earth-ZSM-11 molecular sieve 3.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 85 ° of C, wash 2 times, 120 DEG C are dried, 540 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 145 ° of C dry 2h, microwave treatment 0.9h, 450 ° of C roasting 5h, catalyst Z n load capacity 5wt% of gained, is denoted as catalyst H.
Embodiment 4
By a certain amount of particle diameter 700nm rare earth-ZSM-11 molecular sieve 4.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.8mol/L at a temperature of 85 ° of C, wash 2 times, 120 ° of C are dried, 530 ° of C roasting 4h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 140 ° of C dry 2h, microwave treatment 1.3h, 650 ° of C roasting 3h, catalyst Z n load capacity 6wt% of gained, is denoted as catalyst I.
Embodiment 5
By a certain amount of particle diameter 800nm rare earth-ZSM-11 molecular sieve 4.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.6mol/L at a temperature of 85 ° of C, wash 2 times, 120 ° of C are dried, 530 ° of C roasting 4h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 140 ° of C dry 1.5h, microwave treatment 1.4h, 650 ° of C roasting 2h, catalyst Z n load capacity 7wt% of gained, is denoted as catalyst J.
Embodiment 6
By a certain amount of particle diameter 950nm rare earth-ZSM-11 molecular sieve 1.2 weight % of rare earth-ZSM-11 molecular sieve (content of rare earth account for), exchange 3 times with the ammonium nitrate solution of 0.9mol/L at a temperature of 85 ° of C, wash 2 times, 120 ° of C are dried, 530 ° of C roasting 3h, obtain H-type molecular sieve, then ion exchange zinc supported metal, use zinc acetate solution, 140 ° of C dry 2.5h, microwave treatment 1.2h, 650 ° of C roasting 3h, catalyst Z n load capacity 11wt% of gained, is denoted as catalyst K.
Comparative example 1-5 and embodiment 1～6 reaction evaluating
The catalyst of comparative example 1-5 and embodiment 1 ~ 6 gained is respectively placed in internal diameter be in the fixed bed reactors that flow continuously of 24mm on carry out catalyst performance evaluation, the loadings of catalyst is 20ml, at N2500 ° of C activation it are warmed up to, then at N under atmosphere2Atmosphere drops to reaction temperature, and raw material is dimethyl ether and benzene, and reaction condition is: 1.0MPa, 400 ° of C, weight space velocity 1h-1, dimethyl ether/benzene mole ratio=1/2, continuous reaction time is 10h, reacts under conditions of as shown in table 1, and the cooling of reacted product cooled device carries out gas-liquid separation.Gas and product liquid all form with Agilent 7890A chromatographic system analysis, and product liquid uses PONA capillary column, hydrogen flame detector.Analysis result normalization, obtains dry gas, liquefied gas and product liquid composition.The percent that the present invention uses is weight/mass percentage composition.
Under conditions of such as table 1, dimethyl ether almost all converts.As can be seen from Table 1, obtaining catalyst B from ZSM-5 catalyst A and different preparation method, C, D compare, and on ZSM-11 molecular sieve catalyst F, the conversion ratio of benzene is high, and dry gas is few, and liquid yield is high, and the C7-C9 aromatic hydrocarbons in liquid is many, C10+ heavy aromatics is few；Compared with not having metallic zinc modified catalyst E, the poor conversion of the benzene on catalyst F ~ K is few, and dry gas and liquid yield difference are inconspicuous, but in dry gas and liquefied gas, olefine selective is the highest, and the C7-C9 aromatic hydrocarbons in liquid is more, C10 +Heavy aromatics is substantially few.By with zinc acetate as presoma, ion exchange combines microwave treatment and obtains catalyst F ~ K and all show as good reactivity worth.
Table 1: dimethyl ether and benzene reactivity worth in different catalysts
*: aromatic hydrocarbons.

Claims (6)

1. the preparation method of the catalyst of a dimethyl ether and benzene alkylation, it is characterised in that:
(1) by the superfine rare-earth-ZSM-11 molecular screen primary powder for preparing with 0.5～1.0mol/L nitric acid Ammonium salt solution is in 70～90 DEG C of exchanges, after drying in 500～550 DEG C of roastings 3～5h, makes H-type molecule Sieve；
(2) product obtained by (1) passes through ion exchange carried metal zinc, and the load capacity of metallic zinc is 0.5～12.0wt%, dry 1-3h, microwave treatment 0.2-1.5h, 400-700 in air atmosphere for 120-150 DEG C DEG C roasting 3-6h, prepares required catalyst；
Catalyst prepared by described method is applied to dimethyl ether and benzene and generates high yield by alkylated reaction C7-C9 aromatic hydrocarbons, by-product height selective olefin simultaneously.
2., according to dimethyl ether described in claim 1 and the preparation method of the catalyst of benzene alkylation, it is special Levying and be: in step (1), the particle diameter of described superfine rare-earth-ZSM-11 molecular sieve is 100-1000nm.
3., according to dimethyl ether described in claim 2 and the preparation method of the catalyst of benzene alkylation, it is special Levying and be: in step (1), the particle diameter of described superfine rare-earth-ZSM-11 molecular sieve is 100-600nm.
4., according to dimethyl ether described in claim 1 and the preparation method of the catalyst of benzene alkylation, it is special Levying and be: in step (2), the load capacity of described metallic zinc is 0.5～6.0wt%.
5., according to dimethyl ether described in claim 1 and the preparation method of the catalyst of benzene alkylation, it is special Levy and be: in step (2), described metal zinc source is in zinc acetate.
6., according to dimethyl ether described in claim 1 and the preparation method of the catalyst of benzene alkylation, it is special Levy and be: in step (2), described microwave treatment 0.4-1.0h.
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