CN110721739A - Preparation method of olefin catalyst prepared from methanol - Google Patents

Preparation method of olefin catalyst prepared from methanol Download PDF

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Publication number
CN110721739A
CN110721739A CN201911018110.XA CN201911018110A CN110721739A CN 110721739 A CN110721739 A CN 110721739A CN 201911018110 A CN201911018110 A CN 201911018110A CN 110721739 A CN110721739 A CN 110721739A
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zinc
mixed solution
molecular sieve
methanol
catalyst
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杜成荣
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    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of an olefin catalyst prepared from methanol, which comprises the steps of (1) crushing a molecular sieve and dispersing the molecular sieve in ionized water; (2) adding pseudo-boehmite; (3) dispersing zinc-containing additive and phosphorus-containing additive in ionized water; (4) mixing and grinding; (5) spray vacuum freeze drying; (6) roasting to obtain the methanol-to-olefin catalyst. The preparation method of the olefin catalyst prepared from methanol has the beneficial effects that: the preparation method of the catalyst is simple and easy to implement, and has good repeatability; the prepared catalyst has excellent reaction performance and high mechanical strength.

Description

Preparation method of olefin catalyst prepared from methanol
Technical Field
The invention belongs to the technical field of olefin catalyst preparation, and particularly relates to a preparation method of an olefin catalyst prepared from methanol.
Background
Lower olefins (C)2-C4) Is an important organic chemical raw material and is mainly used for producing plastics and other chemical products. Currently, 98% of the ethylene in the world comes from steam cracking of petroleum-based feedstocks, and propylene is mainly obtained as a co-product of steam cracking to produce ethylene and a byproduct of catalytic cracking. In recent years, with the increasing scarcity of petroleum resources and the increasing surge of prices, the technical route of preparing methanol from low-price coal and natural gas resources and then preparing low-carbon olefins by catalytic conversion of methanol shows more and more economic advantages and attractiveness.
In the prior art, an important catalyst for a process for preparing low-carbon olefin by converting methanol is a silicoaluminophosphate molecular sieve as an active component. Silicon is introduced into a framework of an aluminum phosphate molecular sieve by UCC company in the early eighties of the twentieth century to synthesize the aluminum phosphate molecular sieve. The framework of the silicoaluminophosphate molecular sieve is composed of a phosphorus-oxygen tetrahedron, an aluminum-oxygen tetrahedron and a silicon-oxygen tetrahedron, and the framework is negatively charged. Therefore, when the cation with the balance outside the framework is H +, the molecular sieve has acidity, and can be used as solid acid in catalytic reaction of hydrocarbon cracking, isomerization, alkylation, alcohol dehydration and other carbonium ion mechanisms
However, since the silicoaluminophosphate molecular sieve catalyst needs to be regenerated frequently, certain requirements are made on the abrasion performance and the service life of the silicoaluminophosphate molecular sieve catalyst, but no effective method is available for preparing the catalyst with high strength and high performance.
Disclosure of Invention
The invention aims to provide a preparation method of an olefin catalyst prepared from methanol, which solves the problem of poor wear performance of a silicoaluminophosphate molecular sieve catalyst in the prior art.
The technical scheme adopted by the invention is that the preparation method of the olefin catalyst prepared from methanol is implemented according to the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a sieve with the size less than or equal to 100 meshes to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 2-8 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution, and stirring for 1-2.5 hours at the temperature of 30-45 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 3-6 hours, and grinding to obtain a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and 6, roasting the crude catalyst at 550-700 ℃ for 4-8 h to prepare the olefin catalyst prepared from methanol.
The invention is also characterized in that:
the zinc-containing additive is any one of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, zinc phosphate, zinc phosphite, zinc pyrophosphate and zinc polyphosphate.
The phosphorus-containing additive is any one of phosphoric acid, phosphorous acid, pyrophosphoric acid, aluminum phosphate sol, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite or ammonium dihydrogen phosphite, zinc phosphate, zinc phosphite, zinc pyrophosphate and zinc polyphosphate.
In the step 2, pseudo-boehmite is added into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1: 1.5-2.
Grinding the mixed solution in the step 4 until the particle size of more than 80 percent of solid matters in the mixed solution is less than or equal to 6 mu m.
The invention has the beneficial effects that: the preparation method of the catalyst provided by the invention is simple and easy to implement, and has good repeatability; the prepared chemical has excellent reaction performance and high mechanical strength.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of an olefin catalyst prepared from methanol, which is implemented according to the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a sieve with the size less than or equal to 100 meshes to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 2-8 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1: 1.5-2, and stirring for 1-2.5 h at the temperature of 30-45 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is any one of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, zinc phosphate, zinc phosphite, zinc pyrophosphate and zinc polyphosphate.
Wherein the phosphorus-containing additive is any one of phosphoric acid, phosphorous acid, pyrophosphoric acid, aluminum phosphate sol, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite or ammonium dihydrogen phosphite, zinc phosphate, zinc phosphite, zinc pyrophosphate and zinc polyphosphate.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 3-6 h, grinding until the particle size of more than 80% of solid matters in the third mixed solution is less than or equal to 6 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and 6, roasting the crude catalyst at 550-700 ℃ for 4-8 h to prepare the olefin catalyst prepared from methanol.
The vacuum freeze drying technology is a drying technology which freezes wet materials or solutions into solid at a lower temperature (-10 ℃ to-50 ℃), then directly sublimates water into gas without liquid state under vacuum (1.3-13 Pa), and finally dehydrates the materials. Its main advantage is: (1) the dried material keeps the original chemical composition and physical properties, the moisture in the material is basically sublimated on the frozen solid surface below 0 ℃ for drying, and the material is left in an ice shelf during freezing, so that the dried product has unchanged volume, is loose and porous; (2) the heat consumption is less than other drying methods. Therefore, the prepared catalyst has large specific area and good catalytic effect.
Example 1
A preparation method of an olefin catalyst prepared from methanol specifically comprises the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a 100-mesh sieve to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 8 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1:1.5, and stirring for 2.0 hours at the temperature of 40 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is zinc nitrate.
Wherein the phosphorus-containing additive is phosphoric acid.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 3 hours, grinding until the particle size of more than 80% of solid matters in the third mixed solution is 6 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and step 6, roasting the crude catalyst at 550 ℃ for 6 hours to prepare the olefin catalyst prepared from the methanol.
The catalyst is applied to the reaction of preparing low-carbon olefin by methanol conversion: methanol conversion 93.62%, C in the gas phase product2＝34.58％、C3＝37.67％，C4＝18.01％，C2＝～C4Total 90.26%.
Example 2
A preparation method of an olefin catalyst prepared from methanol specifically comprises the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a 80-mesh sieve to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 7 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1:1.6, and stirring for 1h at 35 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is zinc chloride.
Wherein the phosphorus-containing additive is ammonium phosphate.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 4 hours, grinding until the particle size of more than 80% of solid matters in the third mixed solution is less than or equal to 4 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and step 6, roasting the crude catalyst at the temperature of 600 ℃ for 4 hours to prepare the methanol-to-olefin catalyst.
The catalyst is applied to the reaction of preparing low-carbon olefin by methanol conversion: conversion of methanol was 97.90%, C in the gas phase product2＝37.04％、C3＝34.58％，C4＝19.96％，C2＝～C4Total 91.58%.
Example 3
A preparation method of an olefin catalyst prepared from methanol specifically comprises the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a 60-mesh sieve to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 6 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1:1.7, and stirring for 1.5h at the temperature of 45 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is zinc acetate.
Wherein the phosphorus-containing additive is ammonium dihydrogen phosphite.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 5 hours, grinding until the particle size of more than 80% of solid matters in the third mixed solution is less than or equal to 5 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and step 6, roasting the crude catalyst at 650 ℃ for 8 hours to prepare the methanol-to-olefin catalyst.
The catalyst is applied to the reaction of preparing low-carbon olefin by methanol conversion: methanol conversion rate of 96.89%, C in gas phase product2＝38.79％、C3＝34.96％，C4＝14.15％，C2＝～C4Total 88.08%.
Example 4
A preparation method of an olefin catalyst prepared from methanol specifically comprises the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a 40-mesh sieve to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 3 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1:1.8, and stirring for 2.0 hours at the temperature of 40 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is zinc phosphate.
Wherein the phosphorus-containing additive is zinc polyphosphate.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 6 hours, grinding until the particle size of more than 80% of solid matters in the third mixed solution is less than or equal to 4 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and step 6, roasting the crude catalyst at the temperature of 700 ℃ for 7 hours to prepare the methanol-to-olefin catalyst.
The catalyst is applied to the reaction of preparing low-carbon olefin by methanol conversion: conversion of methanol was 97.88%, C in the gas phase product2＝35.04％、C3＝36.01％，C4＝15.43％，C2＝～C4Total 86.48%.
Example 5
A preparation method of an olefin catalyst prepared from methanol specifically comprises the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a 20-mesh sieve to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 2 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution according to the mass ratio of the molecular sieve to the pseudo-boehmite of 1:2, and stirring for 2.5 hours at 35 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
wherein the zinc-containing additive is zinc phosphite.
Wherein the phosphorus-containing additive is ammonium phosphite.
Step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 5 hours, grinding until the particle size of more than 80% of solid matters in the third mixed solution is less than or equal to 6 microns, and obtaining a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and 6, roasting the crude catalyst at 550-700 ℃ for 5 hours to prepare the olefin catalyst prepared from methanol.
The catalyst is applied to the reaction of preparing low-carbon olefin by methanol conversion: conversion of methanol was 97.21%, C in the gas phase product2＝38.92％、C3＝32.75％，C4＝15.87％，C2＝～C4A total of 87.54%.

Claims (5)

1. The preparation method of the catalyst for preparing the olefin from the methanol is characterized by comprising the following steps:
step 1, crushing a molecular sieve, sieving the crushed molecular sieve by using a sieve with the size less than or equal to 100 meshes to obtain a matrix molecular sieve, dispersing the matrix molecular sieve in ionized water, and stirring for 2-8 hours to obtain a first mixed solution;
step 2, adding pseudo-boehmite into the first mixed solution, and stirring for 1-2.5 hours at the temperature of 30-45 ℃ to obtain a third mixed solution;
step 3, uniformly dispersing the zinc-containing additive and the phosphorus-containing additive in the ionized water to obtain a fourth mixed solution;
step 4, adding the fourth mixed solution into the third mixed solution under the stirring state, stirring for 3-6 hours, and grinding to obtain a fifth mixed solution;
step 5, spraying the fifth mixed solution into liquid nitrogen, and performing vacuum freeze drying to obtain a crude catalyst;
and 6, roasting the crude catalyst at 550-700 ℃ for 4-8 h to prepare the olefin catalyst prepared from methanol.
2. The method of claim 1, wherein the zinc-containing additive is any one of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, zinc phosphate, zinc phosphite, zinc pyrophosphate, and zinc polyphosphate.
3. The method of claim 1, wherein the phosphorus-containing additive is any one of phosphoric acid, phosphorous acid, pyrophosphoric acid, aluminum phosphate sol, diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphite or dihydrogen ammonium phosphite, zinc phosphate, zinc phosphite, zinc pyrophosphate, and zinc polyphosphate.
4. The method for preparing the olefin catalyst from the methanol according to claim 1, wherein in the step 2, the pseudoboehmite is added into the first mixed solution according to the mass ratio of the molecular sieve to the pseudoboehmite of 1: 1.5-2.
5. The method of claim 1, wherein the mixed solution in step 4 is ground until more than 80% of the solid substances have a particle size of less than or equal to 6 μm.
CN201911018110.XA 2019-10-24 2019-10-24 Preparation method of olefin catalyst prepared from methanol Pending CN110721739A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704390A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Method for preparing olefin by conversion of methanol
US20070032378A1 (en) * 2005-08-08 2007-02-08 Karch John A Attrition resistant MTO catalyst
CN105396615A (en) * 2015-10-18 2016-03-16 任丘市华北石油科林环保有限公司 Catalyst for preparing low carbon olefins from methanol
CN107626345A (en) * 2016-07-18 2018-01-26 任丘市华北石油科林环保有限公司 A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst
CN108201899A (en) * 2016-12-16 2018-06-26 惠州市绿孔雀科技股份有限公司 A kind of preparing light olefins from methanol catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704390A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Method for preparing olefin by conversion of methanol
US20070032378A1 (en) * 2005-08-08 2007-02-08 Karch John A Attrition resistant MTO catalyst
CN105396615A (en) * 2015-10-18 2016-03-16 任丘市华北石油科林环保有限公司 Catalyst for preparing low carbon olefins from methanol
CN107626345A (en) * 2016-07-18 2018-01-26 任丘市华北石油科林环保有限公司 A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst
CN108201899A (en) * 2016-12-16 2018-06-26 惠州市绿孔雀科技股份有限公司 A kind of preparing light olefins from methanol catalyst and preparation method thereof

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Application publication date: 20200124