CN101417236A - Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin - Google Patents
Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin Download PDFInfo
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- CN101417236A CN101417236A CNA2007101762746A CN200710176274A CN101417236A CN 101417236 A CN101417236 A CN 101417236A CN A2007101762746 A CNA2007101762746 A CN A2007101762746A CN 200710176274 A CN200710176274 A CN 200710176274A CN 101417236 A CN101417236 A CN 101417236A
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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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention provides a catalyst used for preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol, which is obtained by the modification of zeolite molecular sieve by metal, nonmetal or/and rare earth metal, mixing, spraying, drying and forming of amorphous adhesive containing silicon or aluminium and the zeolite molecular sieve, and decoration of surface acidity and porous structure by siloxane-based compounds, wherein, the content of the alkaline earth metal is 0.1-8wt percent of the total weight of the catalyst, the content of the nonmetal is 0.1-8wt percent of the total weight of the catalyst, the content of the rare earth metal is 0.1-5wt percent of the total weight of the catalyst, and the loading of the Si decorated by the siloxane-based compound is 0.1-10wt percent of the total weight of the catalyst; the catalyst is used for the reaction of preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol; in the products, the selectivity of the para-xylene in the xylene isomers is more than 99 percent and the selectivity of the ethane and propylene in the composition C1-C5 is more than 90 percent.
Description
Technical field
The present invention relates to a kind of alkylation of toluene methanol high selectivity system paraxylene and low-carbon alkene fluid catalyst.It is characterized in that methylbenzene methanol can carry out alkylated reaction and methanol decomposition reaction high selectivity simultaneously and generate paraxylene and ethene, propylene on this catalyst.
Background technology
Paraxylene and ethene are two kinds of base stocks of synthesizing polyester (PET).At present, toluene, C are mainly adopted in paraxylene production
9Aromatic hydrocarbons and mixed xylenes are raw material, produce by disproportionation, isomerization, adsorbing separation or cryogenic separation.Because the paraxylene content in its product is controlled by thermodynamics, paraxylene is at C
8Only account in the BTX aromatics about 20%, material circular treatment amount is big in the technical process, and equipment is huge, the operating cost height.Particularly the boiling point of three isomers of dimethylbenzene differs very little, adopts common distillation technique can not obtain the high-purity paraxylene, and must adopt expensive adsorptive separation technology.Ethene be with crude refining light oil (naphtha and light diesel fuel) and liquefied petroleum gas (LPG) and the natural gas processing ethane and the propane that make be that raw material is produced, mainly depend on petroleum resources.Along with increasing rapidly of global polyester demand, the demand of required two kinds of base stock paraxylene and ethene is cumulative year after year also.
In recent years, domestic and international many patent disclosures the new way of paraxylene and ethylene production, the paraxylene that toluene methylation can the production high selectivity wherein, preparing light olefins from methanol is that non-petroleum path is produced ethene and propylene.USP 3,965, and 207 disclose use ZSM-5 molecular sieve makees catalyst, reaction temperature 500-750 ℃, are about 90% in the high selectivity of 600 ℃ of paraxylene; USP3,965,208 use the element modified ZSM-5 molecular sieve of VA to make catalyst, have suppressed the generation of meta-xylene, mainly generate paraxylene and ortho-xylene, are about 90% in the high selectivity of 600 ℃ of paraxylene; USP 4,250, and 345 use the ZSM-5 molecular sieve of phosphorus and the modification of magnesium dual element to be catalyst, are about 98% in the best selective of 450 ℃ of paraxylene; USP 4,670, and 616 use borosilicate molecular sieve and silica or aluminium oxide to be prepared into catalyst, paraxylene selectivity formula 50-60%; USP4,276,438,4,278,827 use the molecular sieve (SiO of special construction
2/ Al
2O
3≧ 12) also with modifications such as copper, silver, gold or germanium, tin, lead, can obtain the p dialkyl benzene of high selectivity; USP 4,444, and 989 use the pure silicon molecular sieve of crystal type, and make the compound of arsenic phosphorus, magnesium, boron and tellurium carry out modification, have improved the selectivity of paraxylene; USP 4,491, and 678 use crystal type borosilicate and IIA and IIIA element and silicon and phosphorus can improve the selectivity of paraxylene greatly and can improve life of catalyst as common component.USP 5,034, and 362 use SiO
2/ Al
2O
3≧ 12 ZSM-5 and ZSM-11 are catalyst, and carry out roasting being higher than under 650 ℃ the condition, can improve the selectivity of p dialkyl benzene.USP 5,563, and 310 use the acidic molecular sieve that contains the IVB element also to carry out modified catalyst with the metal of VIB, can improve the selectivity of the p dialkyl benzene of alkylation of toluene methanol reaction; USP6,504,072 use the preferred ZSM-5 of mesoporous molecular sieves, and handle being higher than under 950 ℃ the steam, carry out modification with phosphorous oxides then, and the diffusion effect that has proposed the catalyst micropore optionally influences paraxylene; USP 6,613, and 708 use organo-metallic compound that catalyst is carried out modification, can improve the selectivity of p dialkyl benzene greatly.On the other hand, domestic and international many patent disclosures utilize non-petroleum path such as methyl alcohol or dimethyl ether to produce the technology of ethene and propylene.Mobil Oil company in 1976 has carried out methyl alcohol is converted into hydrocarbon on the ZSM-5 molecular sieve catalyst reaction.USP4 discloses methyl alcohol transforms gasoline on the ZSM-5 molecular sieve catalyst process in 035,430; USP4 discloses methyl alcohol is produced low-carbon alkene on the ZSM-5 molecular sieve catalyst technology in 542,252; USP 3,911,041, and USP 4,049,573, USP 4,100,219, JP 60-126233, JP 61-97231 discloses among the JP 62-70324 and EP 6501 and has used the reaction of the ZSM-5 molecular sieve catalyst of phosphorus, magnesium, silicon or alkali metal modification by preparing low carbon olefinic hydrocarbon with methanol; USP 5,367, disclose the reaction that Dalian Chemical Physics Research Institute uses the ZSM-5 molecular sieve catalyst of phosphorus and lanthanum modification to produce low-carbon alkene by methyl alcohol or dimethyl ether in 100, and the overall selectivity of its ethene, propylene and butylene can reach about 85%.
Above-mentioned patent discloses the new way of preparation paraxylene and low-carbon alkene respectively, because two courses of reaction are acid catalyzed reaction, all require the shape selective catalysis effect, therefore all used the modified HZSM-5 molecular sieve as the activity of such catalysts component, but because purpose product difference, there is very big difference again in the characteristics of the catalyst of two processes.A kind of catalyst of preparation satisfies the requirement of alkylation of toluene methanol system paraxylene and methanol-to-olefins simultaneously if employ new technology, and just can be implemented in the course of reaction and produces paraxylene and ethene simultaneously.
On the other hand, alkylation of toluene methanol system paraxylene and be that the reaction for preparing light olefins from methanol of catalyst all adopts fixed bed reaction with the ZSM-5 molecular sieve, because the reaction carbon deposit causes catalysqt deactivation, so fixed bed reaction must frequently switch regeneration, complicated operation.
Summary of the invention
The object of the present invention is to provide a kind of alkylation of toluene methanol high selectivity system paraxylene and low-carbon alkene fluid catalyst.
For achieving the above object, alkylation of toluene methanol system paraxylene provided by the invention and low-carbon alkene fluid catalyst, be by metal, nonmetal with the former powder of zeolite molecular sieve or/and rare-earth metal modified, with the amorphous binding agent mixed atomizing drying and moulding of siliceous or aluminium, obtain through compound-modified surface acidity of siloxy group and pore structure more then; Wherein:
Alkaline earth metal content is the 0.1-8wt% of total catalyst weight;
Nonmetal content is the 0.1-8wt% of total catalyst weight;
Rare earth metal content is the 0.1-5wt% of total catalyst weight;
The loading of the compound-modified back of siloxy group Si is the 1-10wt% of total catalyst weight.
Described catalyst, wherein zeolite molecular sieve is alumino-silicate or the Silicophosphoaluminaand with crystallization skeleton structure, structure type is MFI, MEL or AEL.
Described catalyst, wherein alumino-silicate is that ZSM-5 is or/and ZSM-11 zeolite molecular sieve, preferably ZSM-5; Silicophosphoaluminaand is the SAPO-11 molecular sieve.
Described catalyst, wherein metal is alkaline-earth metal Mg, Ca oxide or its soluble-salt; Nonmetal is phosphorous oxides or phosphoric acid; Rare earth metal is the soluble-salt of lanthanum.
Described catalyst, wherein the siloxy group compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The mixture of one or more that described catalyst, amorphous binding agent wherein siliceous or aluminium are kaolin, clay, aluminium oxide, aluminium colloidal sol, silica and Ludox.
Described catalyst, wherein catalyst is the micro-spherical catalyst of spray shaping.
Catalyst of the present invention is used for producing paraxylene and low-carbon alkene reaction in the alkylation of toluene methanol high selectivity: in fluidized-bed reactor, its reaction temperature is 350-550 ℃, and preferable temperature is 400-500 ℃.
The specific embodiment
Catalyst of the present invention is to be that MFI, MEL or AEL alumino-silicate or Silicophosphoaluminaand are active component with the structure type with crystallization skeleton structure, amorphous binding agent mixed-forming with siliceous or aluminium, by silicone agent its outer surface acidity and duct are modified and be prepared into catalyst, its preparation process is as follows:
1) the former powder of zeolite molecular sieve is prepared into acidic zeolite through exchange, roasting.
2) with acidic zeolite impregnating metal, nonmetal or rare earth metal, obtain modified catalyst.
3) modified catalyst is mixed the back spray drying forming with the amorphous binding agent of siliceous or aluminium, obtain microspherical catalyst.
4) use siloxy group reagent that microspherical catalyst is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain fluidized catalyst.
The used zeolite molecular sieve of the present invention is Si-Al molecular sieve or aluminium silicophosphate molecular sieve, and Si-Al molecular sieve can be selected ZSM-5 for use, the ZSM-11 zeolite molecular sieve; Silicon phosphorus aluminium series molecular sieve can be selected the SAPO-11 molecular sieve for use.
Catalyst of the present invention carries out modification through metal, oxide, soluble-salt nonmetal or rare earth metal to acidic zeolite, and purpose is to improve the reactivity worth of catalyst preparing light olefins from methanol.
The catalyst characteristics of the present invention's preparation is shown in the following general formula of siloxy group compound:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The catalyst of the present invention's preparation is applied to the methylbenzene methanol reaction and produces paraxylene and low-carbon alkene reaction, and its range of reaction temperature is 350-550 ℃, and preferable temperature range is 400-500 ℃.
The abrasion index of fluid catalyst of the present invention is less than 2.
Catalyst of the present invention is applied to the methylbenzene methanol reaction and produces paraxylene and low-carbon alkene (ethene and propylene) reaction, can be by regulating the productive rate that toluene and methanol (mol ratio) ratio changes paraxylene and low-carbon alkene.The selectivity of paraxylene in xylene isomer is greater than 99% in the product, and ethene and propylene are at C
1-C
5Selectivity is greater than 90% in the component.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 (preparation Mg-HZSM-5 fluidized catalyst)
With the former powder (SiO of ZSM-5 zeolite molecular sieve
2/ Al
2O
3=61) remove the template agent 550 ℃ of following roastings, exchange 4 times with ammonium nitrate solution in 80 ℃ of water-baths, the exchange back obtains the HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours.
Use slaine that the HZSM-5 zeolite molecular sieve is carried out modification, step is respectively:
(1) HZSM-5 zeolite molecular sieve 10kg, 9% Mg (MgCl
26H
2O) dipping spends the night, and after the oven dry, 550 ℃ of following roastings 3 hours, obtains the Mg-HZSM-5 zeolite molecular sieve;
(2) the Mg-HZSM-5 zeolite molecular sieve that step 1 is obtained mixes with siliceous or al binder and carries out spray drying forming: 40%Mg-HZSM-5 (butt)+20% Al
2O
3(boehmite)+40%Al
2O
3(aluminium colloidal sol)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.4, obtains the Mg-HZSM-5 fluidized catalyst of microspheroidal;
(3) use the silicone agent tetraethyl orthosilicate that the Mg-HZSM-5 fluid catalyst that step 2 obtains is carried out finishing: 5kg Mg-HZSM-5 fluidized catalyst is put into 5kg tetraethyl orthosilicate dipping and is spent the night, incline liquid after, after 120 ℃ of oven dry, 550 ℃ of roastings 3 hours, obtain modifying back Mg-HZSM-5 fluidized catalyst, be numbered TMFC-01.
Embodiment 2 (preparation Ca-HZSM-5 fluidized catalyst)
(1) HZSM-5 zeolite molecular sieve 10kg, 9% Ca (CaCl
2) flood and spend the night, after the oven dry,, obtain the Ca-HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours;
(2) the Ca-HZSM-5 zeolite molecular sieve that step 1 is obtained mixes with siliceous or al binder and carries out spray drying forming: 40% Ca-HZSM-5 (butt)+20% Al
2O
3(boehmite)+40% kaolin+an amount of biogum, making beating, glue grind, go bubble, spray drying forming, catalyst particle size distribution 20～100 μ m, 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.2, obtains microspheroidal Ca-HZSM-5 fluidized catalyst;
(3) use the silicone agent tetraethyl orthosilicate that the Ca-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing.Step is respectively: 5kg Ca-HZSM-5 microspherical catalyst is put into 5kg tetraethyl orthosilicate dipping spends the night, incline liquid after, after 120 ℃ of oven dry, use solvent wash, 550 ℃ of roastings 3 hours, obtain modifying back Ca-HZSM-5 fluidized catalyst, be numbered TMFC-02.
Embodiment 3 (preparation P-HZSM-5 fluidized catalyst)
(1) HZSM-5 zeolite molecular sieve 20kg, 3% P (H
3PO
4) flood and spend the night, after the oven dry,, obtain the P-HZSM-5 zeolite molecular sieve 550 ℃ of following roastings 3 hours;
(2) 5kg P-HZSM-5 zeolite molecular sieve is mixed with siliceous or al binder carry out spray drying forming, step is respectively: 40% P-HZSM-5 (butt)+20% Al
2O
3(boehmite)+40% SiO
2(Ludox)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.8, obtains the P-HZSM-5 fluidized catalyst of microspheroidal;
(3) use the silicone agent tetraethyl orthosilicate that the P-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing, step is respectively: 5kg P-HZSM-5 microspherical catalyst is put into 5kg tetraethyl orthosilicate dipping spend the night, incline liquid after, after 120 ℃ of oven dry, use solvent wash, 550 ℃ of roastings 3 hours, obtain modifying back P-HZSM-5 fluidized catalyst, be numbered TMFC-03.
Embodiment 4 (preparation P-La-HZSM-5 fluidized catalyst)
(1) gets the P-HZSM-5 zeolite molecular sieve 10kg that step 1 prepares among the embodiment 3,3% La (La (NO
3)
36H
2O) dipping spends the night, and after the oven dry, 550 ℃ of following roastings 3 hours, obtains the P-La-HZSM-5 zeolite molecular sieve;
(2) the P-La-HZSM-5 molecular sieve is mixed with siliceous or al binder carry out spray drying forming, step is respectively: 40% P-La-HZSM-5 (butt)+20% Al
2O
3(boehmite)+40% SiO
2(Ludox)+an amount of biogum, removes bubble, spray drying forming, catalyst particle size 20～100 μ m that distribute at making beating, glue mill, and 550 ℃ of roastings are 3 hours in muffle furnace, and the catalyst abrasion index is 1.7, obtains the P-La-HZSM-5 fluidized catalyst;
(3) use the silicone agent tetraethyl orthosilicate that the P-La-ZSM-5 fluidized catalyst that step 2 obtains is carried out finishing, step is respectively: 5kg P-La-HZSM-5 is put into 5kg tetraethyl orthosilicate dipping spend the night, incline liquid after, after 120 ℃ of oven dry, use solvent wash, 550 ℃ of roastings 3 hours, obtain modifying back P-La-HZSM-5 fluidized catalyst, be numbered TMFC-04.
Embodiment 5 (reaction evaluating)
Be reflected in the medium-sized circulating fluid bed reaction device and carry out.Reaction condition is as follows: loaded catalyst is 5Kg, and the reactor reserve is 1.5Kg, and the catalyst circulation amount is 0.1-5Kg/hr, and reaction temperature is 450 ℃, 600 ℃ of regeneration gas temperature, and raw material toluene: methyl alcohol (mol ratio)=2:1, methylbenzene methanol weight space velocity are 2 hours
-1Adopt Varian 3800 gas-chromatographies, CP-WAX 52CB capillary chromatographic column on-line analysis product distributes (normalization behind the removal toluene), and is as shown in table 1.C wherein
1-C
5Composition analysis adopts Varian 3800 gas-chromatographies, CP-PoraPLOT Q-HT capillary chromatographic column, and the result is as shown in table 2.
Table 1
| Catalyst | TMFC-01 | TMFC-02 | TMFC-03 | TMFC-04 |
| Feed time (min) | 120 | 120 | 120 | 120 |
| Toluene conversion (%) | 13.75 | 13.72 | 16.81 | 20.10 |
| Paraxylene selectivity (%) * | 85.91 | 87.67 | 94.29 | 99.10 |
| Product distribution (%) | ||||
| C 1-C 5 | 6.60 | 5.97 | 16.53 | 28.99 |
| Benzene | 6.40 | 7.14 | 0.83 | 0.08 |
| Ethylbenzene | 2.65 | 1.89 | 0.35 | 0.24 |
| Paraxylene | 65.30 | 62.93 | 70.41 | 64.39 |
| Meta-xylene | 9.04 | 7.59 | 2.41 | 0.00 |
| Ortho-xylene | 1.68 | 1.25 | 1.85 | 0.60 |
| ≧C 9 | 8.34 | 13.23 | 7.62 | 5.70 |
| Add up to | 100.00 | 100.00 | 100.00 | 100.00 |
*The selectivity of paraxylene in xylene isomer
Table 2
| Catalyst | TMFC-01 | TMFC-02 | TMFC-03 | TMFC-04 |
| Feed time (min) | 120 | 120 | 120 | 120 |
| CH 4 | 4.65 | 5.70 | 6.87 | 1.32 |
| C 2H 4 | 47.27 | 46.35 | 49.98 | 52.52 |
| C 2H 6 | 1.04 | 0.92 | 0.90 | 0.05 |
| C 3H 6 | 32.01 | 35.83 | 32.40 | 38.43 |
| C 3H 8 | 5.60 | 2.39 | 1.92 | 0.31 |
| C 4 + | 7.05 | 7.25 | 7.02 | 5.97 |
| C 5 + | 2.39 | 1.55 | 0.90 | 1.40 |
| C 2H 4+C 2H 6 | 79.28 | 82.18 | 82.32 | 90.95 |
Claims (10)
1, a kind of alkylation of toluene methanol system paraxylene and low-carbon alkene fluid catalyst, with zeolite molecular sieve by metal, nonmetal or/and rare-earth metal modified, with the amorphous binding agent mixed atomizing drying and moulding of siliceous or aluminium, obtain through compound-modified surface acidity of siloxy group and pore structure more then; Wherein:
Alkaline earth metal content is the 0.1-8wt% of total catalyst weight;
Nonmetal content is the 0.1-8wt% of total catalyst weight;
Rare earth metal content is the 0.1-5wt% of total catalyst weight;
The loading of the compound-modified back of siloxy group Si is the 1-10wt% of total catalyst weight.
According to the described catalyst of claim 1, it is characterized in that 2, zeolite molecular sieve is alumino-silicate or the Silicophosphoaluminaand with crystallization skeleton structure, structure type is MFI, MEL or AEL.
According to the described catalyst of claim 2, it is characterized in that 3, alumino-silicate is that ZSM-5 is or/and the ZSM-11 zeolite molecular sieve; Silicophosphoaluminaand is the SAPO-11 molecular sieve.
According to the described catalyst of claim 3, it is characterized in that 4, alumino-silicate is ZSM-5.
According to the described catalyst of claim 1, it is characterized in that 5, metal is alkaline-earth metal Mg, Ca oxide or its soluble-salt; Nonmetal is phosphorous oxides or phosphoric acid; Rare earth metal is the soluble-salt of lanthanum.
According to the described catalyst of claim 1, it is characterized in that 6, the siloxy group compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
7, according to the described catalyst of claim 1, it is characterized in that the mixture of one or more that amorphous binding agent siliceous or aluminium is kaolin, clay, aluminium oxide, aluminium colloidal sol, silica and Ludox.
According to the described catalyst of claim 1, it is characterized in that 8, catalyst is the micro-spherical catalyst of spray shaping.
9, each described catalyst of claim 1-8 is produced application in paraxylene and the low-carbon alkene fluidized-bed reaction in the alkylation of toluene methanol high selectivity.
10, according to the described application of claim 9, wherein, its reaction temperature is 350-550 ℃, and preferable temperature is 400-500 ℃.
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|---|---|---|---|
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| CN104128198A (en) * | 2014-07-18 | 2014-11-05 | 陕西煤化工技术工程中心有限公司 | Catalyst for alkylation of toluene with methanol to produce paraxylene with coproduction of ethylene and application thereof |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568913A3 (en) * | 1992-05-03 | 1995-03-22 | Dalian Chemical Physics Inst | Process for the conversion of methanol to light olefins and catalyst used for such process. |
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-
2007
- 2007-10-24 CN CN2007101762746A patent/CN101417236B/en active Active
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