CN101417235A - 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
- Publication number
- CN101417235A CN101417235A CNA2007101762695A CN200710176269A CN101417235A CN 101417235 A CN101417235 A CN 101417235A CN A2007101762695 A CNA2007101762695 A CN A2007101762695A CN 200710176269 A CN200710176269 A CN 200710176269A CN 101417235 A CN101417235 A CN 101417235A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular sieve
- paraxylene
- zeolite molecular
- described catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst used for preparing para-xylene and low-carbon olefin movable bed by selective methylation of toluene with methanol. Molecular sieves with a certain acidity and porous structure are mixed with amorphous adhesive containing silicon or aluminium so as to prepare spherical grains with the size of 1-2mm; subsequently, the acidity is adjusted by using P and La; and then the surface acidity and the porous structure are decorated by siloxane-based compounds so as to obtain the movable bed catalyst. The catalyst is used for the reaction of preparing para-xylene and low-carbon olefin 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 system paraxylene and low-carbon alkene movable bed catalyst.
The invention still further relates to the application of above-mentioned catalyst in alkylation of toluene methanol reaction and methanol decomposition reaction high selectivity generation paraxylene and low-carbon alkene (ethene, propylene).
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 the fixed bed reaction catalyst must frequently switch regeneration, complicated operation.Adopt fluidized-bed reaction technology and fluidized catalyst can overcome the shortcoming that catalyst in the fixed bed reaction technology is easily tied charcoal inactivation and frequent regeneration, but catalyst loss easy to wear in the fluidized reaction, the cost of catalyst increases.
Summary of the invention
The object of the present invention is to provide a kind of alkylation of toluene methanol high selectivity to produce the movable bed catalyst of paraxylene and low-carbon alkene.
For achieving the above object, alkylation of toluene methanol high selectivity system paraxylene provided by the invention and low-carbon alkene movable bed catalyst, be to have the acidity and the zeolite molecular sieve of pore structure and the amorphous binding agent of siliceous or aluminium to be mixed with the globulate particle, use P, its acidity of La modulation then, again through compound-modified its surface acidity of siloxy group and pore structure and obtain;
Wherein the content of P is the 0.1-8wt% of catalyst total amount;
Wherein the content of La is the 0.1-5wt% of catalyst total amount;
Wherein the loading of Si is the 1-10wt% of catalyst total amount behind the silanization.
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, the alumino-silicate that wherein has the crystallization skeleton structure are ZSM-5 or ZSM-11 zeolite molecular sieve, and Silicophosphoaluminaand is the SAPO-11 molecular sieve.
Described catalyst, wherein zeolite molecular sieve is the ZSM-5 zeolite molecular sieve.
Described catalyst, wherein this catalyst is the spheric granules of 1-2mm.
Described catalyst, wherein P is phosphorous oxides or phosphoric acid; La is the soluble-salt of lanthanum.
Described catalyst, wherein 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 mixture of one or more that described catalyst, amorphous binding agent wherein siliceous or aluminium are aluminium oxide, aluminium colloidal sol, silica and Ludox.
Catalyst of the present invention can be used in alkylation of toluene methanol system paraxylene and the low-carbon alkene reaction, and its reaction condition is: in moving-burden bed reactor, reaction temperature is 350-550 ℃, and preferred reaction temperature is 400-500 ℃.
The catalyst of the present invention preparation is produced paraxylene and ethene, propylene in the alkylation of toluene methanol high selectivity, and 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.
Characteristics of the present invention are, in moving bed reaction technology, catalyst slowly moves, and the catalyst near inactivation in the reactor can enter regeneration activating in the regenerator continuously, and therefore continued operation that both can realization response can reduce the wearing and tearing of catalyst again.
The specific embodiment
Alkylation of toluene methanol high selectivity of the present invention is produced paraxylene and low-carbon alkene movable bed catalyst, be that the zeolite molecular sieve that will have certain acidity and pore structure is mixed with into the 1-2mm spheric granules with the amorphous binding agent of siliceous or aluminium, use P, its acidity of La modulation then, obtain movable bed catalyst through compound-modified its surface acidity of siloxy group and pore structure again.
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 to be prepared into catalyst, its preparation process is as follows:
1, the former powder of zeolite molecular sieve is prepared into acidic molecular sieve through ammonium ion exchange, roasting.
2, zeolite molecular sieve is mixed with the amorphous binding agent of siliceous or aluminium, adopt forming oil column or extrusion forming technology that zeolite molecular sieve is prepared into 1-2mm spheric granules catalyst.
3, preformed catalyst is flooded P, La component, obtain modified catalyst.
4, use siloxy group reagent that modified catalyst is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain movable bed catalyst.
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, ZSM-11 and both mixed crystal for use, preferred ZSM-5 zeolite molecular sieve; Silicon phosphorus aluminium series molecular sieve can be selected SAPO-11 for use.
The present invention uses P, La soluble-salt that molecular sieve is carried out modification, and purpose is to improve the reactivity worth of catalyst preparing light olefins from methanol.
P of the present invention is phosphorous oxides or phosphoric acid; La is the soluble-salt of lanthanum.
In the catalyst of the present invention, the content of P is the 0.1-8wt% of total catalyst weight; The content of La is the 0.1-5wt% of total catalyst weight.
Shown in the following general formula of siloxy group compound of the present invention:
R wherein
1, R
2, R
3And R
4Be the alkyl of 1-10 carbon atom, the loading of Si is the 1-10wt% of total catalyst weight behind the silanization.
The mixture of one or more that amorphous binding agent siliceous or aluminium of the present invention is aluminium oxide, aluminium colloidal sol, silica and Ludox.
Catalyst of the present invention is the spheric catalyst of diameter 1-2mm, and this catalyst is used for moving bed reaction.
The catalyst of the present invention's preparation is applied to alkylation of toluene methanol system paraxylene and low-carbon alkene reaction, and its range of reaction temperature is 350-550 ℃, and preferable temperature range is 400-500 ℃.
Catalyst of the present invention is applied to alkylation of toluene methanol system paraxylene and low-carbon alkene reaction, can be by regulating the productive rate that toluene and methanol (mol ratio) ratio changes paraxylene and low-carbon alkene.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1: Preparation of catalysts
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.
HZSM-5 zeolite molecular sieve 10.2kg (butt 68.5%)+Ludox 11.9kg (SiO
225.2%)+and appropriate amount of deionized water, mixing the back extrusion modling is the 2mm spheric granules, obtains moulding HZSM-5 zeolite molecular sieve.
Use P, La that the moulding HZSM-5 zeolite molecular sieve that embodiment 1 obtains is carried out modification, step is respectively:
(1) moulding HZSM-5 zeolite molecular sieve 6kg, 2% P (H
3PO
4) flood and spend the night, after the oven dry,, obtain the P-HZSM-5 molecular sieve 550 ℃ of following roastings 3 hours;
(2) get P-HZSM-5 zeolite molecular sieve 3kg, 2%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.
Use the silicone agent tetraethyl orthosilicate that P-HZSM-5, the P-La-HZSM-5 molecular sieve of moulding HZSM-5, modification are carried out finishing.Step is respectively:
(1) 3Kg HZSM-5 is put into 3kg tetraethyl orthosilicate dipping and spends the night, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back HZSM-5 zeolite molecular sieve 550 ℃ of roastings 3 hours, be numbered TMMC-01.
(2) 3kg P-HZSM-5 is put into 3kg tetraethyl orthosilicate dipping and spends the night, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back P-HZSM-5 zeolite molecular sieve 550 ℃ of roastings 3 hours, be numbered TMMC-02.
(3) 3kg P-La-HZSM-5 is put into 3kg tetraethyl orthosilicate dipping and spends the night, incline liquid after, after 120 ℃ of oven dry,, obtain modifying back P-La-HZSM-5 zeolite molecular sieve 550 ℃ of roastings 3 hours, be numbered TMMC-03.
Embodiment 2: reaction evaluating
On moving-burden bed reactor, carry out the alkylation of toluene methanol reaction, use respectively and be numbered TMMC-01, TMMC-02 and TMMC-03 catalyst among the embodiment 1, reaction condition is as follows: loaded catalyst is respectively 3Kg, the reactor reserve is 1.5Kg, the catalyst circulation amount is 0.1-0.5Kg/ days, reaction temperature is 450 ℃, raw material toluene: methyl alcohol (mol ratio)=2:1.Adopt 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 | TMMC-01 | TMMC-02 | TMMC-03 |
| Feed time (min) | 30 | 30 | 30 |
| Toluene conversion (%) | 19.70 | 20.51 | 21.53 |
| Paraxylene selectivity (%) * | 92.43 | 99.77 | 99.13 |
| Product distribution (%) | |||
| C 1-C 5 | 22.15 | 18.93 | 15.91 |
| Benzene | 0.21 | 0.15 | 0.06 |
| Ethylbenzene | 0.44 | 0.19 | 0.17 |
| Paraxylene | 63.64 | 74.18 | 76.48 |
| Meta-xylene | 2.97 | 0.19 | 0.00 |
| Ortho-xylene | 2.24 | 0.61 | 0.68 |
| ≧C 9 | 8.35 | 5.75 | 6.71 |
| Add up to | 100 | 100 | 100 |
*The selectivity of paraxylene in xylene isomer
Table 2
| Catalyst | TMMC-01 | TMMC-02 | TMMC-03 |
| Feed time (min) | 20-40 | 20-40 | 20-40 |
| CH 4 | 15.22 | 9.62 | 1.33 |
| C 2H 4 | 44.22 | 48.59 | 52.33 |
| C 2H 6 | 0.62 | 0.12 | 0.05 |
| C 3H 6 | 27.08 | 32.24 | 38.89 |
| C 3H 8 | 0.87 | 0.47 | 0.27 |
| C 4 + | 9.18 | 7.47 | 5.86 |
| C 5 + | 2.81 | 1.49 | 1.28 |
| C 2H 4+C 2H 6 | 71.30 | 80.83 | 91.22 |
Claims (10)
1, a kind of alkylation of toluene methanol high selectivity system paraxylene and low-carbon alkene movable bed catalyst, be to have the acidity and the zeolite molecular sieve of pore structure and the amorphous binding agent of siliceous or aluminium to be mixed with the globulate particle, use P, its acidity of La modulation then, again through compound-modified its surface acidity of siloxy group and pore structure and obtain;
Wherein the content of P is the 0.1-8wt% of catalyst total amount;
Wherein the content of La is the 0.1-5wt% of catalyst total amount;
Wherein the loading of Si is the 1-10wt% of catalyst total amount behind the silanization.
2, according to the described catalyst of claim 1, it is characterized in that zeolite molecular sieve is alumino-silicate or the Silicophosphoaluminaand with crystallization skeleton structure, structure type is MFI, MEL or AEL.
3, according to the described catalyst of claim 2, the alumino-silicate that it is characterized in that having the crystallization skeleton structure is ZSM-5, ZSM-11 zeolite molecular sieve, and Silicophosphoaluminaand is the SAPO-11 molecular sieve.
4,, it is characterized in that zeolite molecular sieve is the ZSM-5 zeolite molecular sieve according to the described catalyst of claim 3.
5,, it is characterized in that this catalyst is the spheric granules of 1-2mm according to the described catalyst of claim 1.
6,, it is characterized in that P is phosphorous oxides or phosphoric acid according to the described catalyst of claim 1; La is the soluble-salt of lanthanum.
7,, it is characterized in that shown in the following general formula of siloxy group compound according to the described catalyst of claim 1:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
8, according to the described catalyst of claim 1, the amorphous binding agent that it is characterized in that siliceous or aluminium is one or more a mixture of aluminium oxide, aluminium colloidal sol, silica and Ludox.
9, the application of each described catalyst of claim 1-8 in alkylation of toluene methanol system paraxylene and low-carbon alkene reaction, in moving-burden bed reactor, reaction temperature is 350-550 ℃.
10,, it is characterized in that reaction temperature is 400-500 ℃ according to the described application of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101762695A CN101417235B (en) | 2007-10-24 | 2007-10-24 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101762695A CN101417235B (en) | 2007-10-24 | 2007-10-24 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101417235A true CN101417235A (en) | 2009-04-29 |
| CN101417235B CN101417235B (en) | 2011-05-04 |
Family
ID=40628340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101762695A Expired - Fee Related CN101417235B (en) | 2007-10-24 | 2007-10-24 | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101417235B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780417A (en) * | 2010-02-10 | 2010-07-21 | 中国海洋石油总公司 | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof |
| CN102372589A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Moving bed catalytic process for preparing p-xylene by alkylating aromatic hydrocarbon |
| CN102372588A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing moving bed of para-xylene by aromatics alkylation |
| CN101767038B (en) * | 2010-02-05 | 2012-04-18 | 中国海洋石油总公司 | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application |
| WO2013091335A1 (en) * | 2011-12-19 | 2013-06-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, and preparation method and application of ethylene and propylene |
| CN101607858B (en) * | 2009-07-24 | 2013-07-24 | 中国海洋石油总公司 | Method for preparing aromatic hydrocarbons and propylene simultaneously employing methanol/dimethyl ether |
| CN103638963A (en) * | 2013-12-06 | 2014-03-19 | 陕西煤化工技术工程中心有限公司 | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof |
| 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 |
| CN105772061A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Toluene and methanol and/or dimethyl ether alkylation reaction catalyst and preparation method thereof |
| CN106631676A (en) * | 2016-12-09 | 2017-05-10 | 中国科学院大连化学物理研究所 | Moving bed method for co-producing low-carbon olefin during p-xylene preparation through toluene alkylation |
| CN107519928A (en) * | 2017-08-07 | 2017-12-29 | 江苏师范大学 | A kind of methanol alkylation produces the preparation method of paraxylene catalyst |
| CN107952475A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method of decalin base catalyst |
| US10099973B2 (en) | 2014-06-04 | 2018-10-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing p-xylene and co-producing propylene with high selectivity |
| CN108786905A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | A kind of benzene, methanol alkylation preparing methylbenzene coproduction paraxylene catalyst in-situ preparation method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102764B (en) * | 1985-04-01 | 1988-02-24 | 大连工学院 | Preparation and application of zeolite catalyst modified by rare earth |
| CN85102828A (en) * | 1985-04-01 | 1986-07-23 | 大连工学院 | Produce p-methyl-ethylbenzene with phosphorous modified ZSM-5 catalyst |
| CN1060099C (en) * | 1994-04-18 | 2001-01-03 | 大连理工大学 | Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance |
-
2007
- 2007-10-24 CN CN2007101762695A patent/CN101417235B/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607858B (en) * | 2009-07-24 | 2013-07-24 | 中国海洋石油总公司 | Method for preparing aromatic hydrocarbons and propylene simultaneously employing methanol/dimethyl ether |
| CN101767038B (en) * | 2010-02-05 | 2012-04-18 | 中国海洋石油总公司 | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application |
| CN101780417B (en) * | 2010-02-10 | 2012-04-18 | 中国海洋石油总公司 | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof |
| CN101780417A (en) * | 2010-02-10 | 2010-07-21 | 中国海洋石油总公司 | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof |
| CN102372589B (en) * | 2010-08-23 | 2014-04-23 | 中国石油化工股份有限公司 | Moving bed catalytic process for preparing p-xylene by alkylating aromatic hydrocarbon |
| CN102372589A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Moving bed catalytic process for preparing p-xylene by alkylating aromatic hydrocarbon |
| CN102372588A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing moving bed of para-xylene by aromatics alkylation |
| CN102372588B (en) * | 2010-08-23 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing moving bed of para-xylene by aromatics alkylation |
| AU2012357510B2 (en) * | 2011-12-19 | 2016-03-24 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
| US9844770B2 (en) * | 2011-12-19 | 2017-12-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
| US20150005559A1 (en) * | 2011-12-19 | 2015-01-01 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst used in the production of ethylene and propylene from methanol and/or dimethyl ether, method for preparing the same and method for using the same |
| WO2013091335A1 (en) * | 2011-12-19 | 2013-06-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, and preparation method and application of ethylene and propylene |
| EP2796197A4 (en) * | 2011-12-19 | 2016-08-17 | Dalian Chemical Physics Inst | Catalyst for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, and preparation method and application of ethylene and propylene |
| EA024895B1 (en) * | 2011-12-19 | 2016-10-31 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Catalyst for preparing ethylene and propylene from methanol and/or dimethyl ether, preparation and use thereof |
| CN103638963B (en) * | 2013-12-06 | 2017-01-18 | 陕西煤化工技术工程中心有限公司 | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof |
| CN103638963A (en) * | 2013-12-06 | 2014-03-19 | 陕西煤化工技术工程中心有限公司 | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof |
| US10099973B2 (en) | 2014-06-04 | 2018-10-16 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing p-xylene and co-producing propylene with high selectivity |
| 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 |
| CN105772061B (en) * | 2014-12-26 | 2018-07-20 | 中国科学院大连化学物理研究所 | Toluene and methanol or/and dimethyl ether catalyst for alkylation reaction and preparation method thereof |
| CN105772061A (en) * | 2014-12-26 | 2016-07-20 | 中国科学院大连化学物理研究所 | Toluene and methanol and/or dimethyl ether alkylation reaction catalyst and preparation method thereof |
| CN107952475A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method of decalin base catalyst |
| CN106631676A (en) * | 2016-12-09 | 2017-05-10 | 中国科学院大连化学物理研究所 | Moving bed method for co-producing low-carbon olefin during p-xylene preparation through toluene alkylation |
| CN108786905A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | A kind of benzene, methanol alkylation preparing methylbenzene coproduction paraxylene catalyst in-situ preparation method |
| CN108786905B (en) * | 2017-04-27 | 2020-09-15 | 中国科学院大连化学物理研究所 | In-situ preparation method of catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol |
| CN107519928A (en) * | 2017-08-07 | 2017-12-29 | 江苏师范大学 | A kind of methanol alkylation produces the preparation method of paraxylene catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101417235B (en) | 2011-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101417235B (en) | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin | |
| CN101417236B (en) | Fluid bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin | |
| CN101780417B (en) | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof | |
| CN101417233A (en) | Fixed bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin and use thereof | |
| CN101456784B (en) | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent | |
| CN101767038B (en) | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application | |
| CN101966467B (en) | Catalyst for C8 aromatics isomerization reaction technology and preparation method thereof | |
| CN101456786B (en) | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent | |
| CN101405241B (en) | Selective conversion from oxygen-containing matter to propylene by utilizing moving bed technology and hot liquid stabilization bifunctional catalyst system | |
| CN103157514B (en) | Catalyst for preparing paraxylene by mutual transformation of carbinol and / or dimethyl and C4 liquefied gas, preparation method and application thereof | |
| JP2007051143A (en) | Method for producing lower olefin by using multiple reaction zone | |
| CN101945840A (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| CN101456785B (en) | Method for producing p-xylene and co-producing light olefins with high selectivity | |
| CN102416342A (en) | Catalyst for preparing aromatic hydrocarbon through methanol conversion as well as preparation method and application thereof | |
| CN103459560B (en) | The manufacture method of monocyclic aromatic hydrocarbon | |
| CN104710265B (en) | A kind of method preparing xylol and propylene | |
| CN1721378A (en) | A kind of method of toluene methylation system p-Xylol co-producing light olefins | |
| CN101724432B (en) | Method for producing high-octane gasoline by light hydrocarbon non-hydrogenation modification | |
| CN104710267A (en) | Method for preparing p-xylene and propylene through methanol or/and dimethyl ether | |
| CN104710266A (en) | Method for combined production of low carbon olefins by preparation of p-xylene from methanol or/and dimethyl ether | |
| KR101912398B1 (en) | Method for preparing paraxylene with co-production of propylene with high selectivity | |
| CN107398294A (en) | A kind of preparation method and application of the molecular sieve catalyst of modified no-adhesive ZSM-5-11 | |
| CN100413826C (en) | Method for producing propylene | |
| JP4026047B2 (en) | Process for producing propylene from olefin streams | |
| CN100368359C (en) | Production system for increasing production of propylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20211024 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |