CN114534777B - Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene - Google Patents
Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene Download PDFInfo
- Publication number
- CN114534777B CN114534777B CN202011346659.4A CN202011346659A CN114534777B CN 114534777 B CN114534777 B CN 114534777B CN 202011346659 A CN202011346659 A CN 202011346659A CN 114534777 B CN114534777 B CN 114534777B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular sieve
- polyethylbenzene
- benzene
- reaction
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a molecular sieve catalyst for preparing ethylbenzene by reaction of polyethylbenzene and benzene, belonging to the field of molecular sieve catalysts. The preparation method of the catalyst comprises the following steps: mixing and kneading the silicon dioxide binder and MCM-49 molecular sieve raw powder for molding, and then drying, roasting, exchanging ammonium nitrate solution and drying to obtain ammonium SiO 2 The MCM49 catalyst is dipped in the mixed solution of ammonium fluoride and polyvinyl pyrrolidone (PVP) at a certain temperature, and the FSiO is prepared by further drying and roasting 2 MCM-49 catalyst. Catalyst prepared by the invention and F/SiO prepared by only impregnating ammonium fluoride 2 Compared with MCM-49 catalyst, the conversion rate of benzene and polyethylbenzene on the catalyst can be further improved.
Description
Technical Field
The invention belongs to the field of molecular sieve catalysts, and particularly relates to a preparation method of a molecular sieve catalyst for preparing ethylbenzene by reacting polyethylbenzene and benzene.
Background
Ethylbenzene is a raw material for producing styrene units, and styrene is a raw material for producing polystyrene, styrene-butadiene rubber, and ABS resin. Benzene and ethylene are alkylated under the catalysis of an acidic catalyst to generate ethylbenzene, and the ethylbenzene and the ethylene are continuously alkylated to generate polyethylbenzene such as diethylbenzene and triethylbenzene. This is a series of reactions from acid-site catalyzed alkylation. In order to increase the yield of ethylbenzene, polyethylbenzene produced by the alkylation reaction needs to be subjected to a transalkylation reaction with benzene to produce ethylbenzene.
The traditional ethylbenzene production method is an aluminum trichloride method, i.e. benzene and ethylene are subjected to alkylation reaction to generate ethylbenzene, diethylbenzene, triethylbenzene and the like under the condition of taking aluminum trichloride as a catalyst. The reaction is carried out under the condition of liquid phase, and has the advantages of low reaction temperature, mild operation condition, low content of xylene impurities in the product ethylbenzene and the like. Polyethylbenzene produced by the alkylation reaction includes diethylbenzene, triethylbenzene and the like, and ethylbenzene can be produced by the transalkylation reaction with benzene. However, the aluminum trichloride method has the problems of equipment corrosion, environmental pollution, complex process flow and the like.
CN1097187A discloses a method for preparing diethylbenzene and triethylbenzene in A1Cl at 160 ℃ in an autoclave 3 Transalkylation reaction under the action of vinyl chloride, with a polyethylbenzene conversion of less than 30%.
USP5600048 discloses a liquid phase alkylation-vapor phase transalkylation process for ethylbenzene production using a ZSM-5 molecular sieve as transalkylation catalyst with a single pass conversion of polyethylbenzene of 45%.
CN11811367A, CN1199727A, USP5030786 and so on successively report a method for producing ethylbenzene by a transalkylation reaction of polyethylbenzene and benzene under a liquid phase condition, wherein a catalyst is a Y-type molecular sieve, and the corresponding polyethylbenzene conversion rate can be achieved by adjusting temperature and pressure under the condition of ensuring the liquid phase condition.
CN1096025A and USP4891458 report a process for preparing ethylbenzene by reacting benzene and diethylbenzene under liquid phase conditions, wherein the conversion rate of diethylbenzene is 57% under the conditions of 3.5MPa and 260 ℃ by using HBeta molecular sieve as a catalyst.
USP5600050, CN1128249A and CN1096470A disclose a liquid phase alkylation-liquid phase transalkylation process for producing ethylbenzene which transalkylation process uses the same catalyst as the alkylation catalyst and is characterized by: the catalyst is made of SiO 2 /Al 2 O 3 HBeta molecular sieve of 20-40 weight portions as active component containing chlorine or fluorine in 0.5-10 wt%, and gama-Al as the rest 2 O 3 The transalkylation condition is that the reaction pressure is 3.8MPa, the reaction temperature is 260 ℃, the benzene/alkylbenzene molecular ratio is 5-10 and the liquid weight space velocity is 3h -1 。
CN1207960A discloses a liquid phase alkylation-liquidThe process of producing ethyl benzene by phase alkyl transfer includes the alkyl transfer process with Beta molecular sieve modified with RE or alkali earth metal as catalyst, the temperature 230-280 deg.c, pressure 2.3-4.3 MPa, benzene/polyethylbenzene molar ratio 8-12 and benzene and polyethylbenzene weight space velocity 6-10 hr -1 Under the conditions of (1), the conversion rate of polyethylbenzene is about 45%.
Living forest, etc. [ Living forest, wangyuchuang, zeng Ma, etc. ] liquid-phase transalkylation of diethylbenzene in preparation of ethylbenzene by catalytic cracking of dry gas, industrial catalysis, 2008,16 (10): 139-141]The transalkylation reaction performance of the 3994 catalyst is studied on a heat-insulating fixed bed, and the reaction temperature, the reaction pressure, the mass space velocity of the raw material and the molar ratio of the benzene to the diethylbenzene are 245 ℃, 3.5MPa and 7h respectively -1 And 1, after 189h of reaction, the conversion rate of diethylbenzene is 35 percent, and the selectivity of ethylbenzene is more than 87 percent.
And Liukefeng and the like [ Liukefeng is used for MWW molecular sieve modification research of benzene and low-carbon hydrocarbon alkylation reaction, doctor paper, 3 months in 2013 and university of Chinese academy of sciences ] compare the benzene and diethylbenzene transalkylation reaction performance on an MCM-22 sample before and after alkali treatment, and the alkali treatment increases the content of an acid site B in the sample, so that the benzene and diethylbenzene transalkylation reaction activity, stability and carbon deposition resistance are improved, and the yield of heavy aromatic hydrocarbon is reduced.
MCM-22, alkaline earth modified Y-type zeolite, HY and Beta zeolite molecular sieves were used for studying transalkylation reactions in related patents CN1597110A, CN1359752A, CN1373006A and CN 1373004A. The results show that the conversion rate of diethylbenzene and the selectivity of ethylbenzene on the modified molecular sieve catalyst can respectively reach more than 70 percent and more than 99 percent.
At present, the catalysts adopted for liquid-phase alkylation of polyethylbenzene and benzene are mostly Y, beta and MWW (MCM-22, MCM-49 and MCM-56) molecular sieves, and the additional element modification is conventional load type, so that the elements are unevenly distributed on the surfaces of the molecular sieves, are easy to fall on the outer surfaces and block orifices (particularly, more prominent under the condition of high content of elements), further influence the diffusion of reactants and products in the catalysts, reduce the reaction activity of the catalysts and the like. Especially for the F element, when the content of F supported on MWW molecular sieve is 1.0% or less by weight, it can be obtained by the conventional mannerTo a loading of more than 99%, i.e. the original solution contains 0.5% W of F, and finally the finished solid catalyst can be loaded>0.49% W, while at high loading of F, the actual solid product is only 1.0-1.2% W as the amount of F of 1.5% W is added to the original solution, and the higher the F loading on the finished catalyst, the greater the difference between the F content of the original solution and the actual, which results in a low utilization of the F-containing solution, requiring constant recycling, increasing the catalyst cost, and being environmentally unfriendly due to the high toxicity of F. Thereby reacting NH 4 F is mixed with polyvinylpyrrolidone (PVP), and the F load on the finished catalyst can be greatly improved (the load rate of F) due to the complexation of PVP>99%,0.05-6F% w), and fluorine is more uniformly distributed on the catalyst, so that economy and environmental protection are achieved and the reactivity of the catalyst is likely to be improved. At present, siO is co-impregnated by ammonium fluoride and polyvinyl pyrrolidone (PVP) mixed solution 2 Preparation of FSiO from MCM-49 2 The study of MCM-49 for this process has not been reported. For this, we apply for FSiO 2 The preparation of MCM-49 molecular sieve catalyst is used for preparing ethylbenzene by reacting polyethylbenzene and benzene.
Disclosure of Invention
The invention aims to provide a preparation method of a molecular sieve catalyst for reaction of polyethylbenzene and benzene, which comprises the steps of kneading and molding a silicon dioxide binder and MCM-49 molecular sieve raw powder, and then drying, roasting, exchanging ammonium nitrate solution and drying to obtain ammonium SiO 2 The MCM49 catalyst is dipped in a mixed solution of ammonium fluoride and polyvinylpyrrolidone (PVP) at a certain temperature, and the required FSiO is prepared by further drying and roasting 2 MCM-49 catalyst. The specific preparation method of the catalyst comprises the following steps:
(1) Mixing and kneading silicon dioxide binder (preferably selected from silica sol and beer silica gel) and MCM-49 molecular sieve raw powder for molding, and then drying, roasting, exchanging ammonium nitrate solution and drying to obtain ammonium SiO 2 MCM49 catalyst wherein the weight percentage of silica in the mixture of MCM-49 molecular sieve and silica is from 10 to 50% (preferably from 20 to 40%). Wherein the drying temperature is 120 ℃, the roasting temperature is 500 ℃, and the concentration of ammonium nitrate solution is 0.5mol/l。
(2) Soaking the catalyst in 30-60 deg.C mixed solution of ammonium fluoride and polyvinylpyrrolidone (PVP) for 0.5-2h, wherein fluorine and PVP are in ammonium form of SiO 2 The weight percentage of the MCM49 catalyst is respectively 0.5-6% (preferably 1.0-1.5%) and 0.5-4% (preferably 1-3%), and the FSiO is further prepared by drying at 100-120 ℃ and roasting at 350-500 ℃ for 2-4 h 2 MCM-49 catalyst.
The application of molecular sieve catalyst for preparing ethylbenzene by the reaction of polyethylbenzene and benzene comprises the following reaction conditions: the pressure is 3.0-4.0MPa, the temperature is 200-260 ℃, the weight ratio of benzene to polyethylbenzene is 2-8, and the weight space velocity of polyethylbenzene is 0.1-1.5h -1 。
The invention has the advantages that:
the method for adding polyvinyl pyrrolidine (PVP) into the ammonium fluoride impregnation liquid solves the problems that F is unevenly distributed on the surface of the molecular sieve and is easy to fall on the outer surface and block orifices after the molecular sieve is impregnated and loaded with F, so that the diffusion of reactants and products in the catalyst is influenced, the reaction activity of the catalyst is reduced and the like.
The catalyst prepared by the invention can be applied to the process of preparing ethylbenzene by the reaction of polyethylbenzene and benzene, and F/SiO impregnated with ammonium fluoride only 2 Compared with MCM-49 catalyst, the conversion rate of benzene and polyethylbenzene on the catalyst can be obviously improved.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Comparative example 1
Weighing 11.76 g of MCM-49 molecular sieve raw powder (85 wt%), adding 6.25 g of 40% (40 wt%) silica sol, mixing, extruding, molding, drying at 120 ℃, roasting at 530 ℃ for 3h, exchanging 0.5mol/l of ammonium nitrate for roasting at 500 ℃ for 3h, and recording the obtained catalyst as Cat-A.
Comparative example 2
Weighing 11.76 g of MCM-49 molecular sieve raw powder (85 wt%), adding 6.25 g of silica sol (40 wt%), mixing, extruding, molding, drying at 120 ℃, roasting at 530 ℃ for 3h, exchanging 0.5mol/l ammonium nitrate for drying at 120 ℃, then soaking in 0.243 g of ammonium fluoride solution at 60 ℃ for 2h, drying and roasting at 500 ℃ for 3h to obtain a catalyst which is marked as Cat-B, and XRF results show that the fluorine weight content in the sample is 1.0%.
Example 1
11.76 g of MCM-49 molecular sieve raw powder (the weight content is 85 percent) is weighed, 6.25 g of silica sol (the weight content is 40 percent) is added and mixed, the mixture is extruded and molded, the mixture is dried at 120 ℃ and roasted at 530 ℃ for 3 hours, then the mixture is exchanged by 0.5mol/l ammonium nitrate and dried at 120 ℃, then the mixture is soaked in 0.243 g of ammonium fluoride mixed solution at 60 ℃ for 0.13g of PVP mixed solution for 2h, the catalyst is obtained by drying at 120 ℃ and roasting at 500 ℃ for 3 hours, the catalyst is marked as Cat-C, and the XRF result shows that the fluorine weight content in the sample is 1.0 percent.
Example 2
Weighing 11.76 g of MCM-49 molecular sieve raw powder (85 wt%), adding 12 g of silica sol (40 wt%), mixing, extruding, molding, drying at 120 ℃ and roasting at 530 ℃ for 3h, exchanging 0.5mol/l of ammonium nitrate for drying at 120 ℃, then soaking in a mixed solution containing 0.58 g of ammonium fluoride at 30 ℃ and 0.59g of PVP, drying at 120 ℃ and roasting at 500 ℃ for 3h to obtain a catalyst which is recorded as Cat-D, and XRF results show that the fluorine weight content in the sample is 2.0%.
Example 3
Weighing 11.76 g of MCM-49 molecular sieve raw powder (the weight content is 85%), adding 8 g of beer silica gel, mixing, extruding, molding, drying at 120 ℃, roasting at 530 ℃ for 3h, exchanging ammonium nitrate by 0.5mol/l for drying at 120 ℃, then soaking in 0.09g of PVP mixed solution containing 0.070 g of ammonium fluoride at 45 ℃ for 0.5h, drying at 120 ℃ and roasting at 500 ℃ for 3h to obtain a catalyst which is recorded as Cat-E, and XRF results show that the weight content of fluorine in the sample is 0.2%.
Example 4
17.65 g of MCM-49 molecular sieve raw powder (85% by weight) is weighed, 2.5 g of silica sol (40% by weight) and 1g of beer silica gel are mixed, extruded and molded, dried at 120 ℃ and roasted at 530 ℃ for 3 hours, then the mixture is subjected to exchange of 0.5mol/l ammonium nitrate for drying at 120 ℃, then the mixture is immersed in a mixed solution containing 2g of ammonium fluoride at 50 ℃ and 0.51g of PVP for 1 hour, the catalyst obtained by drying at 120 ℃ and roasting at 500 ℃ for 3 hours is marked as Cat-F, and XRF results show that the fluorine content in the sample is 6.0% by weight.
Comparative examples 1 to 2 and examples 1 to 4 reaction evaluation:
the evaluation of the reaction properties was carried out on a fixed-bed reactor, 2g of the catalyst being placed in a constant-temperature zone in the middle of a stainless steel reactor (internal diameter 12mm, length 50 cm). Catalyst before reaction in N 2 Activating at 450 deg.C for 1h, cooling, and adding N when the temperature of catalyst bed is 10 deg.C lower than the preset reaction temperature 2 The reaction system was brought to the reaction pressure, and a mixed solution prepared in a certain weight ratio of benzene/polyethylbenzene (95/5 weight ratio of diethylbenzene and triethylbenzene) was fed into the reactor by a pump while the temperature was adjusted to the reaction temperature, to start the transalkylation reaction.
The experimental results in Table 1 show that the SiO compound is pure 2 Compared with MCM-49 molecular sieve catalyst (Cat-A), F/SiO is prepared by conventional load F 2 The conversion rate of benzene and polyethylbenzene on MCM-49 (Cat-B) catalyst can be improved to a certain extent, and FSiO prepared by adopting mixed solution of ammonium fluoride and PVP for impregnation 2 Compared with the conversion rate of Cat-B, the conversion rates of benzene and polyethylbenzene on MCM-49 (Cat-C to Cat-F) can be obviously improved.
TABLE 1 catalyst reactivity
Claims (8)
1. A preparation method of a molecular sieve catalyst for reaction of polyethylbenzene and benzene is characterized in that a silicon dioxide binder and MCM-49 molecular sieve raw powder are kneaded and molded, and then the mixture is dried, roasted, exchanged and dried by ammonium nitrate solution to obtain ammonium SiO 2 MCM49 catalyst, impregnating the catalyst with fluorine at a certain temperatureDissolving ammonium chloride and polyvinylpyrrolidone PVP in a mixed solution, further drying and roasting to obtain the required FSiO 2 MCM-49 catalyst; the weight percentage content of the silicon dioxide in the mixture of the MCM-49 molecular sieve raw powder and the silicon dioxide is 10 to 50 percent;
the ammonium form of SiO 2 The MCM49 catalyst is soaked at 30-60 deg.c for 0.5-2 hr.
2. The method of claim 1, wherein the SiO in the form of ammonium is used to prepare a molecular sieve catalyst for the reaction of polyethylbenzene and benzene 2 In the MCM49 catalyst dipping mixed solution, the weight of fluorine is 0.2-6.0% of the weight of the catalyst, and the weight of polyvinylpyrrolidone PVP is 0.5-4% of the weight of the catalyst.
3. The method of claim 1, wherein the FSiO is a molecular sieve catalyst for the reaction of polyethylbenzene and benzene 2 The drying temperature of the MCM-49 molecular sieve catalyst is 100 to 120 ℃; the roasting temperature is 350-500 ℃, and the roasting time is 2-4 h.
4. A process for preparing a molecular sieve catalyst for the reaction of polyethylbenzene and benzene as claimed in claim 1 wherein: the silica binder used is selected from the group consisting of silica sol, beer silica gel or mixtures thereof.
5. A process for preparing a molecular sieve catalyst for the reaction of polyethylbenzene and benzene as claimed in claim 1 wherein: the weight percentage of the silicon dioxide in the mixture of MCM-49 molecular sieve raw powder and the silicon dioxide is 20 to 40 percent.
6. A process for preparing a molecular sieve catalyst for the reaction of polyethylbenzene and benzene as claimed in claim 1 wherein: ammonium form of SiO 2 The mixed impregnation liquid of the MCM49 catalyst contains 1.0-1.5 wt% of fluorine and 1-3 wt% of polyvinylpyrrolidone PVP.
7. A catalyst prepared by the process of any one of claims 1 to 6.
8. Use of a catalyst according to claim 7 in the reaction of polyethylbenzene and benzene, characterized in that:
the conditions of the catalyst for the reaction of the polyethylbenzene and the benzene are as follows: the pressure is 3.0-4.0MPa, the temperature is 200-260 ℃,
the weight ratio of benzene to polyethylbenzene is 2-8:1, the weight space velocity of the polyethylbenzene is 0.1 to 1.5h -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011346659.4A CN114534777B (en) | 2020-11-26 | 2020-11-26 | Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011346659.4A CN114534777B (en) | 2020-11-26 | 2020-11-26 | Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114534777A CN114534777A (en) | 2022-05-27 |
| CN114534777B true CN114534777B (en) | 2023-04-14 |
Family
ID=81659713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011346659.4A Active CN114534777B (en) | 2020-11-26 | 2020-11-26 | Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114534777B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5600050A (en) * | 1994-12-14 | 1997-02-04 | Chinapetro-Chemical Corp. | Zeolite catalyst for the liquid phase alkylation and transalkylation of benzene |
| CN1171096A (en) * | 1994-12-27 | 1998-01-21 | 美孚石油公司 | Continuous process for preparing ethylbenzene using liquid phase alkylation and vapour phase transalkylation |
| CN1597110A (en) * | 2003-09-16 | 2005-03-23 | 中国科学院大连化学物理研究所 | Catalyst for producing ethyl benzene from multi ethyl benzene and benzene |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN111111758A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Catalyst for preparing toluene and/or xylene by liquid-phase methylation and preparation method thereof |
-
2020
- 2020-11-26 CN CN202011346659.4A patent/CN114534777B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5600050A (en) * | 1994-12-14 | 1997-02-04 | Chinapetro-Chemical Corp. | Zeolite catalyst for the liquid phase alkylation and transalkylation of benzene |
| CN1171096A (en) * | 1994-12-27 | 1998-01-21 | 美孚石油公司 | Continuous process for preparing ethylbenzene using liquid phase alkylation and vapour phase transalkylation |
| CN1597110A (en) * | 2003-09-16 | 2005-03-23 | 中国科学院大连化学物理研究所 | Catalyst for producing ethyl benzene from multi ethyl benzene and benzene |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN111111758A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Catalyst for preparing toluene and/or xylene by liquid-phase methylation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114534777A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101722035B (en) | Catalyst with shape selecting function | |
| US5990031A (en) | Zeolite catalyst with enhanced dealkylation activity and method for producing same | |
| CN101987298B (en) | Metal-modified eutectic zeolite catalyst with EUO (Europium Oxide) structure as well as preparation method and application thereof | |
| CN102205251B (en) | Molecular sieve P-IM-5 and application thereof in toluene alkylation reaction | |
| CN101541419A (en) | Catalyst for xylene isomerization and process for preparing the same | |
| ZA200600889B (en) | Boron selectivation of molecular sieve catalysts and use thereof in hydrocarbon conversion | |
| CN101722020A (en) | Eutectic zeolite catalyst containing EUO structure and preparation method and application thereof | |
| CN101584991B (en) | Catalyst for olefin catalytic cracking to produce propylene and ethylene and application thereof | |
| CN100473461C (en) | Catalyst for C4 liquefied petroleum gas aromatization and preparing method thereof | |
| CN101987969B (en) | Method for converting C9+ heavy arenes into light arenes | |
| CN111111758B (en) | Catalyst for preparing toluene and/or xylene by liquid phase methylation and preparation method thereof | |
| CN101352690A (en) | Preparation method and use of molecular sieve catalyst for producing phenylethane from alkylation of benzene with dilute ethylene | |
| CN114534777B (en) | Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene | |
| CN102500413A (en) | n-butane hydroisomerization catalyst, and preparation method and application thereof | |
| CN113385215B (en) | Preparation method and application of catalyst for preparing propane by hydro-upgrading | |
| CN114433220B (en) | Preparation method of benzene and synthesis gas alkylation catalyst | |
| CN104276924A (en) | Shape-selective disproportionation method of toluene and ethylbenzene | |
| CN102373069A (en) | Method used for C6-alkane cracking | |
| CN112023978B (en) | Xylene isomerization catalyst and preparation method and application thereof | |
| CN114849769B (en) | Catalyst for synthesizing thymol and preparation method and application thereof | |
| CN114425412B (en) | Non-hydroisomerization catalyst for alkyl aromatic hydrocarbon, and preparation method and application thereof | |
| CN115888800B (en) | Shape-selective catalyst for diethylbenzene and preparation method and application thereof | |
| CA1157889A (en) | Ethyltoluene isomer mixtures | |
| CN113509956B (en) | Molecular sieve catalyst, preparation method and application thereof | |
| CN108262058B (en) | Process for selective cracking of non-aromatic hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |