CN113070099B - Phosphorus modified deactivated titanium-silicon molecular sieve catalyst - Google Patents

Phosphorus modified deactivated titanium-silicon molecular sieve catalyst Download PDF

Info

Publication number
CN113070099B
CN113070099B CN202110311999.1A CN202110311999A CN113070099B CN 113070099 B CN113070099 B CN 113070099B CN 202110311999 A CN202110311999 A CN 202110311999A CN 113070099 B CN113070099 B CN 113070099B
Authority
CN
China
Prior art keywords
molecular sieve
phosphorus
modified
mfi structure
titanium
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
Application number
CN202110311999.1A
Other languages
Chinese (zh)
Other versions
CN113070099A (en
Inventor
刘月明
林玉霞
黄鑫
徐德义
余云开
李芳�
张莲霖
陈贞
何鸣元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China Normal University
Original Assignee
East China Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by East China Normal University filed Critical East China Normal University
Priority to CN202110311999.1A priority Critical patent/CN113070099B/en
Publication of CN113070099A publication Critical patent/CN113070099A/en
Application granted granted Critical
Publication of CN113070099B publication Critical patent/CN113070099B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a phosphorus modified deactivated titanium silicalite molecular sieve catalyst, which is prepared by mixing a compound solution containing phosphorus with a deactivated titanium silicalite molecular sieve with an MFI structure by adopting an impregnation method. The phosphorus modified deactivated titanium-silicon molecular sieve is used as an active component of a solid acid catalyst, shows higher propylene/ethylene ratio of a product and lower alkane and arene selectivity of a byproduct than an unmodified deactivated titanium-silicon molecular sieve in the reaction processes of propylene preparation through olefin cracking reaction, propylene preparation through methanol catalytic conversion and the like, and is beneficial to efficient utilization of raw materials. The inactivated titanium-silicon molecular sieve with MFI structure is obtained by conventional drying and roasting after reaction inactivation in the industrial production process of cyclohexanone oxime production from cyclohexanone ammoximation. The phosphorus modified deactivated titanium silicalite molecular sieve catalyst obtained by the invention has stable catalytic performance and good repeatability; the preparation process is simple, the operation is convenient, and the industrial production is easy.

Description

Phosphorus modified deactivated titanium-silicon molecular sieve catalyst
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a phosphorus modified deactivated titanium silicalite molecular sieve catalyst and a preparation method thereof, in particular to a phosphorus modified deactivated titanium silicalite molecular sieve catalyst, wherein a deactivated titanium silicalite molecular sieve with an MFI structure is subjected to phosphorus modification by adopting an impregnation method, and the catalyst is applied to protonic acid catalytic processes such as preparation of propylene by catalytic cracking of carbon tetraolefin and preparation of propylene by catalytic conversion of methanol.
Background
Propylene is an important chemical industry basic raw material, is mainly used for producing polypropylene, acrylonitrile, propylene oxide, isopropanol, epichlorohydrin, acrylic acid, acetone and derivatives thereof and the like, and the demand of the propylene is in a rapidly increasing trend. The carbon tetraolefin is a byproduct of an FCC device in an ethylene production plant and an oil refinery, is usually used as a low-added-value product such as liquefied gas fuel and the like, and is generated into propylene and ethylene through a catalytic cracking reaction, so that the carbon tetraolefin is fully beneficial to byproduct olefin resources. Meanwhile, with the rapid development of Methanol To Olefin (MTO) technology, the technical route for preparing low-carbon olefins such as propylene by catalytic conversion based on methanol as a raw material becomes an effective supplement for preparing low-carbon olefins by a petroleum-based technical route, and a good situation of common development is presented at present. The core of the reaction process of preparing propylene by catalytic cracking of carbon tetraolefin and preparing propylene by catalytic conversion of methanol is the research and development of a high-performance molecular sieve catalyst, the core of the molecular sieve catalyst is an active component molecular sieve of the molecular sieve, and the commonly used molecular sieve is ZSM-5, ZSM-11, FER, ZSM-48, SAPO-34 or a mixture of the ZSM-5, the ZSM-11, the FER, the ZSM-48, the SAPO-34 or the mixture of the ZSM-11, and the like.
Titanium silicalite molecular sieve TS-1 molecular sieve with MFI structure is disclosed since the first publication of patent US 4410501, and has attracted people's attention due to its excellent catalytic oxidation performance. At present, TS-1 molecular sieve is used as a catalyst and H2O2Is a mild reaction system of an oxidant, shows high activity and selectivity in the aspects of organic oxidation reactions such as olefin epoxidation, ketone ammoximation, alkane oxidation, alcohol oxidation and the like, and a byproduct is only an environment-friendly green chemical process of water. Researches find that the fresh titanium-silicon molecular sieve basically does not have protonic acid property, but reacts in the industrial production process of producing cyclohexanone oxime from cyclohexanone ammoximationThe deactivated titanium-silicon molecular sieve with MFI structure has protonic acid property. ZL201810358245.X discloses a method for preparing propylene by catalytic cracking of carbon tetraolefin, which is characterized in that an inactivated titanium silicalite molecular sieve with an MFI structure is adopted as an active component of a catalyst, and the catalyst shows catalytic activity equivalent to that of a modified ZSM-5 molecular sieve and higher propylene selectivity. ZL201810373937.3 discloses a method for preparing propylene by catalyzing methanol, which is characterized in that an inactivated titanium silicalite molecular sieve with an MFI structure is used as an active component of a catalyst, and has a catalytic effect of catalyzing methanol to prepare low-carbon olefin.
Disclosure of Invention
The invention aims to provide a phosphorus modified deactivated titanium silicalite molecular sieve catalyst and a preparation method thereof, wherein the method adopts a phosphorus modified deactivated titanium silicalite molecular sieve with an MFI structure as an active component of the catalyst, and unexpectedly discovers that the catalyst shows high propylene/ethylene ratio of a product and low alkane and arene selectivity of byproducts in the catalytic process of preparing propylene and preparing propylene by catalytic conversion of methanol by catalytic cracking of carbon tetraolefin compared with the unmodified deactivated titanium silicalite molecular sieve with the MFI structure, so that the carbon resource is fully utilized, and the economic principle of green chemical carbon atoms is met.
The purpose of the invention is realized as follows:
a phosphorus modified deactivated titanium silicon molecular sieve catalyst is characterized in that the catalyst comprises 20 to 80 weight percent of molecular sieve and a balance binder, the molecular sieve is a phosphorus modified deactivated titanium silicon molecular sieve with MFI structure or a mixture of the phosphorus modified deactivated titanium silicon molecular sieve with MFI structure and a phosphorus modified ZSM-5 molecular sieve, and the binder is at least one of silicon dioxide, aluminum oxide and aluminum phosphate; the weight percentage of the phosphorus modified deactivated titanium silicon molecular sieve with MFI structure in the molecular sieve mixture is at least 10%; the weight content of phosphorus in the phosphorus-modified inactivated titanium-silicon molecular sieve with MFI structure in the catalyst is 0.05-2.0%; the inactivated titanium-silicon molecular sieve with MFI structure in the catalyst is obtained by carrying out conventional drying and roasting after reaction inactivation in the industrial production process of producing cyclohexanone oxime by cyclohexanone ammoximation.
The preparation process of the phosphorus modified deactivated titanium silicalite molecular sieve with MFI structure is as follows:
firstly, dipping a compound solution containing 0.1-3.0% of phosphorus by weight into a deactivated titanium-silicon molecular sieve with an MFI structure at room temperature-100 ℃ for 1-24 hours to obtain the dipped deactivated titanium-silicon molecular sieve, wherein the phosphorus compound is at least one of phosphoric acid and soluble phosphate;
and secondly, drying the impregnated inactivated titanium silicalite molecular sieve obtained in the first step at 80-110 ℃ for 2-24 hours, and roasting at 500-600 ℃ for 2-24 hours to obtain the phosphorus modified inactivated titanium silicalite molecular sieve with an MFI structure.
The catalyst of the present invention is prepared by molding methods well known to those skilled in the art, for example, by kneading metered amounts of the molecular sieve and the binder, extruding the kneaded mixture to form a molded catalyst, and then performing conventional drying, calcination, etc. to obtain the catalyst.
Compared with the prior art, the invention has the following remarkable advantages:
1. the phosphorus modified deactivated titanium-silicon molecular sieve is used as an active component of the catalyst, the catalyst has stable quality, high propylene/ethylene ratio in a catalytic product, low alkane and arene selectivity and good repeatability.
2. Simple process, convenient operation and easy industrial production.
Detailed Description
All the embodiments are operated according to the operation steps of the technical scheme.
The inactivated titanium-silicon molecular sieve with MFI structure is obtained by conventional drying and roasting after reaction inactivation in the industrial production process of cyclohexanone oxime production from cyclohexanone ammoximation. The phosphorus modified ZSM-5 molecular sieve can be a commercial product or prepared according to the existing literature. In the technical embodiment of the invention, the phosphorus modified ZSM-5 molecular sieve is prepared by taking ZSM-5 with a silicon-aluminum molecular ratio of 42 as a parent according to a method of a document (Journal of Catalysis 309 (2014) 136-145) to obtain the phosphorus modified ZSM-5 molecular sieve with the phosphorus content of 1.9 wt%.
In the technical embodiment of the invention, butene is used as a carbon tetraene probe molecule, and a fixed bed reactor is used for reaction to illustrate the technical effect of protonic acid catalysis of the catalyst.
Example 1
Step one, isovolumetrically dipping the inactivated titanium-silicon molecular sieve with an MFI structure in a compound solution containing phosphorus with the weight content of 0.7 percent, wherein the dipping temperature is room temperature, the dipping time is 8 hours, and the dipped inactivated titanium-silicon molecular sieve is obtained, and the phosphorus compound is phosphoric acid;
secondly, drying the impregnated inactivated titanium silicalite molecular sieve obtained in the first step at 110 ℃ for 12 hours, and roasting at 550 ℃ for 24 hours to obtain a phosphorus-modified inactivated titanium silicalite molecular sieve with an MFI structure, wherein the phosphorus content is 0.49% by weight;
the phosphorus modified deactivated titanium silicalite molecular sieve catalyst is prepared by mixing 70 wt% of the phosphorus modified deactivated titanium silicalite molecular sieve with MFI structure obtained in the above steps and balance weight of alumina, extruding and molding after kneading, and then performing conventional drying and roasting processes.
Example 2
The procedure was as in example 1, except that:
in the first step, a compound solution containing 0.1% phosphorus by weight content is subjected to isovolumetric impregnation of the inactivated titanium-silicon molecular sieve with MFI structure to obtain a phosphorus-modified inactivated titanium-silicon molecular sieve with MFI structure containing 0.05% phosphorus by weight content.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 3
The procedure was as in example 1 except that:
in the first step, a compound solution containing 3.0% phosphorus by weight of phosphorus is subjected to isovolumetric impregnation of the inactivated titanium-silicon molecular sieve with an MFI structure to obtain a phosphorus-modified inactivated titanium-silicon molecular sieve with an MFI structure, wherein the phosphorus content by weight of phosphorus is 2.0%.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 4
The procedure was as in example 1 except that:
in the first step, a compound solution containing 1.5% phosphorus by weight of phosphorus is soaked in the inactivated titanium silicalite molecular sieve with the MFI structure in the same volume, so as to obtain the phosphorus-modified inactivated titanium silicalite molecular sieve with the MFI structure, wherein the phosphorus content by weight of phosphorus is 1.0%.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 5
The procedure was as in example 1 except that:
in the first step, the phosphorus compound is diammonium phosphate.
Further preparing the phosphorus modified deactivated titanium silicon molecular sieve catalyst.
Example 6
The procedure was as in example 1 except that:
in the first step, the phosphorus compound is ammonium dihydrogen phosphate.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 7
The procedure was as in example 1 except that:
in the first step, a compound solution containing 0.7% phosphorus by weight of phosphorus is soaked in the inactivated titanium-silicon molecular sieve with the MFI structure in the same volume, the soaking temperature is room temperature, and the soaking time is 24 hours, so that the impregnated inactivated titanium-silicon molecular sieve is obtained.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 8
The procedure was as in example 1 except that:
in the first step, a compound solution containing 0.7% phosphorus by weight of phosphorus is soaked in the inactivated titanium-silicon molecular sieve with the MFI structure in the same volume, the soaking temperature is 80 ℃, and the soaking time is 1 hour, so that the impregnated inactivated titanium-silicon molecular sieve is obtained.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 9
The procedure was as in example 1 except that:
the phosphorus modified deactivated titanium-silicon molecular sieve catalyst consists of 35 wt% of phosphorus modified deactivated titanium-silicon molecular sieve with MFI structure, 35 wt% of phosphorus modified ZSM-5 molecular sieve and balance alumina.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 10
The procedure was as in example 1 except that:
the phosphorus modified deactivated titanium-silicon molecular sieve catalyst consists of 35 wt% of phosphorus modified deactivated titanium-silicon molecular sieve with MFI structure, 35 wt% of phosphorus modified ZSM-5 molecular sieve and the balance of aluminium phosphate.
Further preparing the phosphorus modified deactivated titanium-silicon molecular sieve catalyst.
Example 11
The procedure was as in example 1 except that:
the phosphorus modified deactivated titanium-silicon molecular sieve catalyst is composed of 35 wt% of phosphorus modified deactivated titanium-silicon molecular sieve with MFI structure, 35 wt% of phosphorus modified ZSM-5 molecular sieve, and balance of alumina (50%) and silica (50%).
Comparative example 1
The catalyst is prepared by mixing and kneading 70 wt% of inactivated titanium-silicon molecular sieve with MFI structure without phosphorus modification and balance alumina, then extruding and molding, and then conventionally drying and roasting.
Example 12
Using butylene as raw material, at 500 deg.C, 0.1MPa of reaction pressure and 6h of weight space velocity-1The performance of the protonic acid catalytic reaction of the catalyst of the invention is examined under the condition of (1), and when the reaction is stably carried out for 1.5 hours, the reaction result is shown in the table.
Results of evaluation of Table reaction
Figure BDA0002989787200000051
From the evaluation of the reaction results, it can be seen that, compared with comparative example 1, the catalyst prepared by phosphorus modification of the deactivated titanium silicalite molecular sieve with MFI structure shows high propylene/ethylene ratio of the product and low C as a by-product1 0～C5 0Alkane and C6 +Selectivity to aromatic hydrocarbons, C5 ＝～C6 ＝The selectivity of olefin is obviously increased, and the olefin carbon resource is effectively utilized.

Claims (1)

1. The phosphorus-modified deactivated titanium silicalite molecular sieve catalyst for preparing propylene by catalytic cracking of carbon tetraolefin is characterized in that the catalyst comprises 20-80 wt% of a molecular sieve and a balance binder, the molecular sieve is a phosphorus-modified deactivated titanium silicalite molecular sieve with an MFI structure or a mixture of the phosphorus-modified deactivated titanium silicalite molecular sieve with the MFI structure and a phosphorus-modified ZSM-5 molecular sieve, and the binder is at least one of silicon dioxide, aluminum oxide and aluminum phosphate; the weight percentage of the phosphorus modified deactivated titanium silicalite molecular sieves with MFI structure in the mixture of molecular sieves is at least 10%; the weight content of phosphorus in the phosphorus-modified deactivated titanium-silicon molecular sieve with an MFI structure in the catalyst is 0.05-2.0%; the inactivated titanium-silicon molecular sieve with MFI structure in the catalyst is obtained by performing conventional drying and roasting after reaction inactivation in the industrial production process of producing cyclohexanone oxime by cyclohexanone ammoximation; wherein:
the preparation process of the phosphorus modified deactivated titanium silicalite molecular sieve with MFI structure is as follows:
firstly, dipping a deactivated titanium-silicon molecular sieve with an MFI structure in a compound solution containing phosphorus with the weight content of 0.1-3.0%, wherein the dipping temperature is room temperature-100 ℃, the dipping time is 1-24 hours, so as to obtain the dipped deactivated titanium-silicon molecular sieve, and the phosphorus compound is at least one of phosphoric acid and soluble phosphate;
and secondly, drying the impregnated inactivated titanium-silicon molecular sieve obtained in the first step at 80-110 ℃ for 2-24 hours, and roasting at 500-600 ℃ for 2-24 hours to obtain the phosphorus-modified inactivated titanium-silicon molecular sieve with an MFI structure.
CN202110311999.1A 2021-03-24 2021-03-24 Phosphorus modified deactivated titanium-silicon molecular sieve catalyst Active CN113070099B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110311999.1A CN113070099B (en) 2021-03-24 2021-03-24 Phosphorus modified deactivated titanium-silicon molecular sieve catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110311999.1A CN113070099B (en) 2021-03-24 2021-03-24 Phosphorus modified deactivated titanium-silicon molecular sieve catalyst

Publications (2)

Publication Number Publication Date
CN113070099A CN113070099A (en) 2021-07-06
CN113070099B true CN113070099B (en) 2022-11-01

Family

ID=76613836

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110311999.1A Active CN113070099B (en) 2021-03-24 2021-03-24 Phosphorus modified deactivated titanium-silicon molecular sieve catalyst

Country Status (1)

Country Link
CN (1) CN113070099B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602011A (en) * 2009-07-08 2009-12-16 华东师范大学 A kind of renovation process of titanium-silicon molecular sieve catalyst
CN104512906A (en) * 2013-09-29 2015-04-15 中国石油化工股份有限公司 Titanium-silicon molecular sieve and preparation method thereof
CN107973308A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of phosphorous MFI structure molecular sieve and preparation method thereof
CN108689788A (en) * 2018-04-20 2018-10-23 华东师范大学 A kind of method that C _ 4 alkene catalytic pyrolysis prepares propylene
CN109180409A (en) * 2018-06-27 2019-01-11 华东师范大学 A kind of method of catalysis methanol propylene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7145051B2 (en) * 2002-03-22 2006-12-05 Exxonmobil Chemical Patents Inc. Combined oxydehydrogenation and cracking catalyst for production of olefins

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602011A (en) * 2009-07-08 2009-12-16 华东师范大学 A kind of renovation process of titanium-silicon molecular sieve catalyst
CN104512906A (en) * 2013-09-29 2015-04-15 中国石油化工股份有限公司 Titanium-silicon molecular sieve and preparation method thereof
CN107973308A (en) * 2016-10-21 2018-05-01 中国石油化工股份有限公司 A kind of phosphorous MFI structure molecular sieve and preparation method thereof
CN108689788A (en) * 2018-04-20 2018-10-23 华东师范大学 A kind of method that C _ 4 alkene catalytic pyrolysis prepares propylene
CN109180409A (en) * 2018-06-27 2019-01-11 华东师范大学 A kind of method of catalysis methanol propylene

Also Published As

Publication number Publication date
CN113070099A (en) 2021-07-06

Similar Documents

Publication Publication Date Title
US9260356B2 (en) Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process
CN103157502B (en) Catalyst of preparing ethylene and propylene by carbinol and / or dimethyl ether, preparing method and application thereof
CN101602013A (en) The method of modifying of TS-1 titanium-silicon molecular sieve catalyst
CN102557066A (en) Tetraethoxysilane modified datolite molecular sieve and preparation method and application thereof
EP3827898A1 (en) Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof
CN106694029A (en) Nonmetal modified catalyst and preparation method for same
CN111217656B (en) Catalyst for reaction of preparing 1, 3-butadiene from ethanol and preparation and application thereof
CN113070099B (en) Phosphorus modified deactivated titanium-silicon molecular sieve catalyst
CN106607089A (en) Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application
CN108689788B (en) Method for preparing propylene by catalytic cracking of carbon tetraolefin
CN109180409B (en) Method for preparing propylene by catalyzing methanol
CN105439826B (en) A kind of preparation method of propylene glycol monomethyl ether
CN104557377B (en) The method of oxygenatedchemicals and naphtha coupled reaction production ethylene and propylene
CA2945115A1 (en) Processes for producing aromatic hydrocarbon, p-xylene and terephthalic acid
JP5001274B2 (en) Production method of lower olefins under negative pressure
CN113385215B (en) Preparation method and application of catalyst for preparing propane by hydro-upgrading
CN103418425A (en) Catalyst for propylene preparation through methanol conversion, and preparation method thereof
CN112675902B (en) Catalyst for preparing propylene by inverse disproportionation of ethylene and butene and preparation method thereof
CN115518683A (en) Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic anhydride by durene gas-phase oxidation
CN107999125B (en) Preparation and application of microporous-mesoporous-containing Ti-MWW molecular sieve with core-shell structure
CN107986295B (en) Silicon-containing molecular sieve and preparation method thereof
CN1990436A (en) Process for preparing ethylene, propylene and aromatic hydrocarbons by C4 alkene catalytic conversion
CN110773226A (en) Method for catalyzing fusel oil conversion by using core-shell structure molecular sieve catalyst
CN107954811B (en) Process for converting oxygen-containing organic compounds to carbon-tetrads
CN113509956B (en) Molecular sieve catalyst, preparation method and application thereof

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