CN116082150A - Method for synthesizing (methyl) tert-butyl acrylate by using composite metal oxide catalyst - Google Patents

Method for synthesizing (methyl) tert-butyl acrylate by using composite metal oxide catalyst Download PDF

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CN116082150A
CN116082150A CN202211617913.9A CN202211617913A CN116082150A CN 116082150 A CN116082150 A CN 116082150A CN 202211617913 A CN202211617913 A CN 202211617913A CN 116082150 A CN116082150 A CN 116082150A
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solution
catalyst
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stirring
acrylic acid
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黄家辉
苗治理
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a method for synthesizing tert-butyl (methyl) acrylate by using a composite metal oxide catalyst, belonging to the technical field of organic synthesis. The invention mixes catalyst, polymerization inhibitor, (methyl) acrylic acid and isobutene in a reaction kettle to synthesize (methyl) tert-butyl acrylate, wherein the catalyst is composite oxide WO 3 /Ce x Fe y M z O 2 Wherein M is one or more than two of Zr, nb, sn, ga, re, Y, la, nd, sm, er, and the polymerization inhibitor is a combination of tert-butanol, phenothiazine, p-hydroxyanisole and tert-butylcatechol and is combined with air. The invention obviously reduces the production cost of the tert-butyl acrylateThe method improves the esterification rate, effectively prevents the polymerization of raw materials and products in the reaction process, and has the advantages of simple process route, mild reaction conditions, easy separation of the catalyst and the raw materials and products, and the like.

Description

Method for synthesizing (methyl) tert-butyl acrylate by using composite metal oxide catalyst
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing (methyl) tert-butyl acrylate by using a composite metal oxide catalyst.
Technical Field
The tert-butyl acrylate is an extremely important chemical basic raw material and intermediate, and has unique and strong polar molecules, unsaturated double bonds and carboxylic ester (-COOR) structures, so that a plurality of polymer formulas with good performance can be derived, and the prepared various tert-butyl acrylate polymers have the excellent characteristics of strong cohesiveness, good transparency and clear film formation. Therefore, the tert-butyl acrylate has excellent light stability, weather resistance, water resistance, oil resistance, chemical resistance and other good chemical and physical properties.
In the traditional esterification reaction in industry, acrylic acid and tertiary butanol are mostly synthesized by esterification under the catalysis of concentrated sulfuric acid, and in the reaction process, the tertiary butanol has larger steric hindrance, so that the elimination reaction is more prone to be carried out in the two competitive reactions of esterification and elimination, and the esterification rate is low. The method has the advantages of multiple side reactions, dark product color, complex post-treatment process, serious equipment corrosion and large wastewater discharge.
The acid alkene addition method is a method for producing tert-butyl acrylate products by using more at present, belongs to a typical green chemical atom economic process, and uses abundant and cheap isobutene to replace tert-butyl alcohol, so that the reaction conversion rate is improved, and the production cost is reduced. Compared with the traditional inorganic acid such as concentrated sulfuric acid, sulfonic acid and the like, the process adopts the solid acid catalyst, reduces the corrosion to equipment, is easy to separate products, and can be recycled.
Patent CN104276948A discloses an acidic cationic resin catalyst used in an acid-alkene addition reaction, but the catalyst has low activity, quick deactivation and low reaction selectivity; patent CN110950760 a discloses a p-toluenesulfonic acid catalyst used in acid-alkene addition reaction, but the method adopts a homogeneous catalyst, the later separation process is complex, and the purity of acrylic ester is not high. In addition, in the production process of tert-butyl acrylate, the special structure of raw materials and products determines whether the raw materials and the products are continuous or batch processes, and due to the mixing non-uniformity, the problem of polymerization exists in a reaction system and a refining system all the time, so that research and development of a novel catalyst system for rapidly and efficiently preparing high-purity tert-butyl acrylate is an important subject to be researched at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing tert-butyl (methyl) acrylate by using a composite metal oxide catalyst.
In order to achieve the purpose of the invention, the technical scheme provided by the invention is as follows:
by means of WO 3 /Ce x Fe y M z O 2 Method for synthesizing tert-butyl (methyl) acrylate by using catalyst, WO (WO) 3 /Ce x Fe y M z O 2 Catalyst, polymerization inhibitor, (methyl) acrylic acid and isobutene are mixed in a reaction kettle to synthesize tert-butyl (methyl) acrylate, WO 3 /Ce x Fe y M z O 2 M in the catalyst is one or more than two of Zr, nb, sn, ga, re, Y, la, nd, sm, er.
Based on the technical proposal, further, ceO is used 2 With Fe 2 O 3 Total mass, WO 3 The content is 0.1-30%, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x+y+z=1.
Based on the technical proposal, further, ceO is used 2 With Fe 2 O 3 Total mass, WO 3 The content is 1-20%.
Based on the technical scheme, further, the polymerization inhibitor is combined with air, wherein the polymerization inhibitor is a combination of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 10-15:4-6:2-4:4-6.
Based on the technical scheme, further, the mass ratio of the tert-butyl alcohol to the phenothiazine to the para-hydroxyanisole to the tert-butylcatechol is 12:5:3:5.
Based on the technical scheme, further, the reaction temperature is 30-60 ℃, the air pressure is 0.1-5.0MPa, the reaction time is 2-10h, and the stirring speed is 500-1500rpm.
Based on the technical scheme, further, the mol ratio of the (methyl) acrylic acid to the isobutene is 0.2:1-5:1.
Based on the technical scheme, further, the polymerization inhibitor is 0.01-1% of the mass of the (methyl) acrylic acid.
Based on the technical scheme, further, the mass of the catalyst is 5-20% of the mass of the (methyl) acrylic acid.
Based on the above technical solution, further, the (meth) acrylic acid includes acrylic acid and methacrylic acid; t-butyl (meth) acrylate includes t-butyl acrylate and t-butyl methacrylate.
Based on the technical scheme, the preparation method of the catalyst further comprises the following steps:
1) Weighing soluble salts of Ce, fe and M, adding deionized water, stirring and dissolving to obtain a solution A;
2) Weighing soluble salt of W, adding deionized water, and stirring for dissolution to obtain solution B;
3) Slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished;
4) Weighing a certain amount of template agent CTAB, adding deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2-6 hours after dripping is finished;
5) Slowly dripping a precipitant into the solution obtained in the step 4) under stirring until the pH value is 9-14, and continuously stirring for 2-10h;
6) Transferring the solution obtained in the step 5) into a hydrothermal kettle, and crystallizing for 6-96h at 70-180 ℃;
7) Centrifuging after crystallization, washing until no chloride ions exist, washing for 1-5 times by using absolute ethyl alcohol, and vacuum drying to obtain a precursor;
8) Roasting the precursor in air atmosphere at 400-1100 deg.c for 2-12 hr to obtain composite oxide WO 3 /Ce x Fe y M z O 2 。
Based on the technical scheme, further, the ratio of the template agent to the total mole number of the metal ions in the step 4) is 1:1-1:20.
Based on the technical scheme, further, the precipitant in the step 5) is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Na 2 CO 3 、NaOH、One or more of ammonia water and urea.
Based on the technical scheme, the crystallization temperature in the step 6) is 100-150 ℃ and the crystallization time is 48-96h.
Based on the technical scheme, further, the roasting temperature in the step 8) is 500-700 ℃ and the roasting time is 4-10h.
Compared with the prior art, the invention has the following advantages:
1) The catalyst disclosed by the invention is simple to prepare, good in repeatability and high in reaction esterification rate and selectivity;
2) According to the invention, the composite oxide is used as a catalyst, and a special catalytic system consisting of a plurality of polymerization inhibitors and oxygen-containing nitrogen is used for catalyzing (methyl) acrylic acid and isobutene to synthesize (methyl) tert-butyl acrylate, so that the esterification rate of (methyl) acrylic acid and tert-butyl acrylate can be remarkably improved, and meanwhile, the polymerization problem of raw materials and products in the reaction process can be effectively prevented;
3) The method has the advantages of simple and environment-friendly process, no waste acid or waste water generation, no waste acid or waste water treatment, real atomic economical reaction and production cost reduction.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Example 1
And (3) preparing a catalyst:
13.05g Ce (NO) was weighed out 3 ) 3 ·6H 2 O、6.08g Fe(NO 3 ) 3 ·6H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 1.28g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished;weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.8 Fe 0.2 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 2
And (3) preparing a catalyst:
10.42g Ce (NO) was weighed out 3 ) 3 ·6H 2 O、5.16g ZrOCl2·8H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 1.30g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for several times after crystallization, washing to no chloride ion, and washing with small amount of absolute ethanolWashing 3 times; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.6 Zr 0.4 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 3
And (3) preparing a catalyst:
weigh 12.16g Ce (NO) 3 ) 3 ·6H 2 O、6.46g Fe(NO 3 ) 3 ·6H 2 O、1.29g ZrOCl 2 ·8H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 4.37g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.7 Fe 0.2 Zr 0.1 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 4
And (3) preparing a catalyst:
weigh 12.16g Ce (NO) 3 ) 3 ·6H 2 O、6.46g Fe(NO 3 ) 3 ·6H 2 O、3.51g Nd(NO 3 ) 3 ·6H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 1.59g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.7 Fe 0.2 Nd 0.1 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 5
And (3) preparing a catalyst:
weigh 12.16g Ce (NO) 3 ) 3 ·6H 2 O、6.46g Fe(NO 3 ) 3 ·6H 2 O、3.56g Sm(NO 3 ) 3 ·6H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 1.60g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.7 Fe 0.2 Sm 0.1 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 6
And (3) preparing a catalyst:
weigh 12.16g Ce (NO) 3 ) 3 ·6H 2 O、6.46g Fe(NO 3 ) 3 ·6H 2 O、1.05g SnCl 4 Adding 100ml of deionized water, stirring and dissolving to obtain a solution A; 1.43g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Ce 0.7 Fe 0.2 Sn 0.1 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 7
And (3) preparing a catalyst:
3.51g of Nd (NO) 3 ) 3 ·6H 2 O、2.1g SnCl 4 Adding 100ml of deionized water, stirring and dissolving to obtain a solution A; weighing 0.83g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 1.75g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 deg.c for 6 hr to obtain solid super acid catalyst WO 3 /Nd 0.5 Sn 0.5 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Example 8
And (3) preparing a catalyst:
10.42g Ce (NO) was weighed out 3 ) 3 ·6H 2 O、6.46g Fe(NO 3 ) 3 ·6H 2 O、3.51g Nd(NO 3 ) 3 ·6H 2 O、1.05g SnCl 4 Adding 100ml of deionized water, stirring and dissolving to obtain a solution A; weighing 1.57g of ammonium metatungstate, adding 50ml of deionized water, and stirring for dissolution to obtain a solution B; slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; precursor of solid super acidRoasting the solid super acid catalyst WO in air at 600 deg.c for 6 hr 3 /Ce 0.6 Fe 0.2 Nd 0.1 Sn 0.1 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Comparative example 1
13.05g Ce (NO) was weighed out 3 ) 3 ·6H 2 O、6.08g Fe(NO 3 ) 3 ·6H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution A, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 ℃ for 6 hours to obtain the solid super acid catalyst Ce 0.8 Fe 0.2 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Comparative example 2
And (3) preparing a catalyst:
10.42g Ce (NO) was weighed out 3 ) 3 ·6H 2 O、5.16g ZrOCl 2 ·8H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 4.37g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution A, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 4 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 ℃ for 6 hours to obtain the solid super acid catalyst Ce 0.6 Zr 0.4 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Comparative example 3
And (3) preparing a catalyst:
3.51g of Nd (NO) 3 ) 3 ·6H 2 O、2.1g SnCl 4 Adding 100ml of deionized water, stirring and dissolving to obtain a solution A; weighing 1.75g of template CTAB, adding 50mL of deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution A, and continuing stirring for 4 hours after dripping is finished; slowly dropwise adding 0.1mol/l (NH) under stirring 4 ) 2 CO 3 The precipitant is mixed with ammonia water in equal volume until the pH value is 13,stirring is continued for 4 hours; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 72 hours in an environment of 120 ℃; centrifuging for many times after crystallization, washing until no chloride ions exist, and washing for 3 times by using a small amount of absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid super acid precursor; roasting the solid super acid precursor in air at 600 ℃ for 6 hours to obtain the solid super acid catalyst Nd 0.5 Sn 0.5 O 2 。
Reaction evaluation:
adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Comparative example 4
Putting acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle by taking p-toluenesulfonic acid as a catalyst, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and synthesizing tert-butyl acrylate at the stirring speed of 800 rpm; wherein the molar ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
Comparative example 5
Adding acrylic acid, a catalyst, a polymerization inhibitor and liquid isobutene into a reaction kettle by taking acidic cationic resin as a catalyst, stirring and reacting for 4 hours under the conditions that the temperature is 35 ℃ and the air pressure is 1.0MPa, and stirring at a speed of 800rpm to synthesize tert-butyl acrylate; wherein the mass ratio of the acrylic acid to the polymerization inhibitor to the isobutene is 10:0.01:5.5, the mass of the catalyst is 10% of the mass of the acrylic acid, and the polymerization inhibitor is a mixture of tert-butyl alcohol, phenothiazine, para-hydroxyanisole and tert-butyl catechol, and the mass ratio is 12:5:3:5.
The t-butyl acrylate prepared in the examples and comparative examples was tested using conventional experiments and regulations in the art to determine the esterification rate, and the specific results are shown in table 1, wherein:
the esterification rate at the olefin excess is calculated according to formula (1):
esterification rate= (acid value of 1-reaction system/acid value of reaction pre-system) 100% (1);
when the acid is excessive, the esterification rate is converted according to the mole ratio of the olefine acid, and is calculated as shown in a formula (2):
esterification rate= [ (1) esterification rate/molar ratio of olefine acid ]. 100% (2).
The product selectivity was calculated from the ratio of the chromatographic peak areas and the results are shown in Table 1.
TABLE 1 esterification rate and t-butyl acrylate selectivity for examples 1-8 and comparative examples 1-5
Description of the embodiments Catalyst Esterification rate% T-butyl acrylate selectivity%
Example 1 WO 3 /Ce 0.8 Fe 0.2 O 2 85.8 92.4
Example 2 WO 3 /Ce 0.6 Zr 0.4 O 2 73.6 94.6
Example 3 WO 3 /Ce 0.7 Fe 0.2 Zr 0.1 O 2 85.0 97.7
Example 4 WO 3 /Ce 0.7 Fe 0.2 Nd 0.1 O 2 93.3 96.3
Example 5 WO 3 /Ce 0.7 Fe 0.2 Sm 0.1 O 2 92.6 95.2
Example 6 WO 3 /Ce 0.7 Fe 0.2 Sn 0.1 O 2 92.1 93.5
Example 7 WO 3 /Nd 0.5 Sn 0.5 O 2 88.3 95.4
Example 8 WO 3 /Ce 0.6 Fe 0.2 Nd 0.1 Sn 0.1 O 2 98.5 97.9
Comparative example 1 Ce 0.8 Fe 0.2 O 2 37.1 95.3
Comparative example 2 Ce 0.6 Zr 0.4 O 2 25.3 96.2
Comparative example 3 Nd 0.5 Sn 0.5 O 2 52.6 95.7
Comparative example 4 Para-toluene sulfonic acid 82.6 94.8
Comparative example 5 Acidic cationic resins 90.5 95.4
As can be seen from the results in Table 1, compared with the comparative example, the preparation method of the invention significantly improves the esterification rate of the esterification reaction, reduces the reaction temperature, makes the reaction milder, more green and economical, effectively prevents the polymerization of raw materials and products in the reaction process, and improves the selectivity of the products.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. By means of WO 3 /Ce x Fe y M z O 2 A process for synthesizing tert-butyl (meth) acrylate by using a catalyst, characterized in that WO is used 3 /Ce x Fe y M z O 2 Catalyst, polymerization inhibitor, (methyl) acrylic acid and isobutene are mixed in a reaction kettle to synthesize tert-butyl (methyl) acrylate, WO 3 /Ce x Fe y M z O 2 M in the catalyst is one or more than two of Zr, nb, sn, ga, re, Y, la, nd, sm, er.
2. The method according to claim 1, wherein the catalyst is represented by CeO 2 With Fe 2 O 3 Total mass, WO 3 The content is 0.1-30%, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x+y+z=1.
3. The method according to claim 1, wherein the polymerization inhibitor is used in combination with air, wherein the polymerization inhibitor is a combination of tert-butanol, phenothiazine, para-hydroxyanisole and tert-butylcatechol in a mass ratio of 10-15:4-6:2-4:4-6.
4. The method according to claim 1, wherein the reaction temperature is 30-60 ℃, the air pressure is 0.1-5.0MPa, the reaction time is 2-10h, and the stirring rate is 500-1500rpm.
5. The process of claim 1, wherein the molar ratio of (meth) acrylic acid to isobutylene is from 0.2:1 to 5:1; the polymerization inhibitor is 0.01-1% of (methyl) acrylic acid; the mass of the catalyst is 5-20% of the mass of the (methyl) acrylic acid.
6. The method according to claim 1, wherein the (meth) acrylic acid comprises acrylic acid and methacrylic acid; t-butyl (meth) acrylate includes t-butyl acrylate and t-butyl methacrylate.
7. The method according to claim 1, wherein the method for preparing the catalyst comprises the steps of:
1) Weighing soluble salts of Ce, fe and M, adding deionized water, stirring and dissolving to obtain a solution A;
2) Weighing soluble salt of W, adding deionized water, and stirring for dissolution to obtain solution B;
3) Slowly dripping the solution A into the solution B under stirring, and obtaining a solution C after the dripping is finished;
4) Weighing a certain amount of template agent CTAB, adding deionized water, stirring and dissolving to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2-6 hours after dripping is finished;
5) Slowly dripping a precipitant into the solution obtained in the step 4) under stirring until the pH value is 9-14, and continuously stirring for 2-10h;
6) Transferring the solution obtained in the step 5) into a hydrothermal kettle, and crystallizing for 6-96h at 70-180 ℃;
7) Centrifuging after crystallization, washing until no chloride ions exist, washing for 1-5 times by using absolute ethyl alcohol, and vacuum drying to obtain a precursor;
8) Roasting the precursor in air atmosphere at 400-1100 deg.c for 2-12 hr to obtain composite oxide WO 3 /Ce x Fe y M z O 2 。
8. The method of claim 7, wherein the ratio of the total moles of template to metal ions in step 4) is 1:1 to 1:20; the precipitant in step 5) is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Na 2 CO 3 One or more of NaOH, ammonia water or urea.
9. The method according to claim 7, wherein the crystallization temperature in step 6) is 100-150 ℃ and the crystallization time is 48-96 hours.
10. The method according to claim 7, wherein the firing temperature in step 8) is 500 to 700 ℃ and the firing time is 4 to 10 hours.
CN202211617913.9A 2022-12-15 2022-12-15 Method for synthesizing (methyl) tert-butyl acrylate by using composite metal oxide catalyst Pending CN116082150A (en)

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