CN108558660A - A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate - Google Patents
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate Download PDFInfo
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- CN108558660A CN108558660A CN201810382259.5A CN201810382259A CN108558660A CN 108558660 A CN108558660 A CN 108558660A CN 201810382259 A CN201810382259 A CN 201810382259A CN 108558660 A CN108558660 A CN 108558660A
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- exchange resin
- cation exchange
- rare earth
- benzyl acetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- 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
- Y02P20/584—Recycling of catalysts
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, with styrene, divinylbenzene is raw material, Archon is prepared using initiator B PO suspension polymerisations, the concentrated sulfuric acid and 1 are used again, sulphur ball is made in 2 dichloromethane, it is impregnated again with rare-earth salt solution and rare earth modified cation exchange resin is made, make catalyst with it, with benzyl alcohol, glacial acetic acid is that esterification raw material prepares benzyl acetate, in esterification reaction process, reaction temperature is low, catalyst corrodes equipment small, environmental pollution is small, it is environmentally protective, catalyst high recycling rate, simplify product last handling process.
Description
Technical field
The invention belongs to benzyl acetate preparing technical fields, and in particular to a kind of rare earth modified catalyzing cation exchange resin
The method of synthetic benzyl acetate.
Background technology
Benzyl acetate is a kind of colourless liquid, has fruit fragrant and has Jasmine fragrance, and smell is fresh and sweet also known as acetic acid
Benzene methyl, benzyl acetate, a kind of colourless transparent liquid that its sterling shows, common product are colourless to weak yellow liquid, often
Containing micro chlorine, there are the jasmin of simple and elegant smelling good and pure and fresh fruit aroma taste.Currently, industrially mainly being urged with sulfuric acid
Change esterification process to synthesize, using the concentrated sulfuric acid as catalyst, perishable aging equipment, catalyst, solvent etc. recycle complicated cumbersome, energy
Consumption and pollution environment are big etc..Although it is cheap and easy to get in the choosing of numerous catalyst, because its have it is very strong
Then corrosivity is easy to cause side reaction and is also seriously polluted to environment, and then causes people to its synthetic method
Improved attention.Replace the research of traditional sulfuric acid catalyst very universal with solid acid catalyst in the esterification reaction,
In solid acid include mainly heteropoly acid, solid super-strong acid, ion exchange resin etc..Catalyst is prepared as traditional dipping
Method, but it is few with one or two kinds of rare earth ion modified synergic resins report, and temporarily have no that document report rare earth ion is modified
Polystyrene storng-acid cation exchange resin is used for Catalytic Synthesis of Benzyl Acetate.
Invention content
The object of the present invention is to provide a kind of environmental-friendly rare earth modified catalyzing cation exchange resin synthesis of acetic acid benzyls
The method of ester.
The present invention is achieved by the following technical solutions.
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, including following operating procedure:
(1) after mixing styrene and divinylbenzene according to the ratio that molar ratio is 7.14: 1, it is heated to 38-42 DEG C, then
The initiator B PO of styrene quality 2.0-3.0% is added thereto, 5-10min is persistently stirred in heat preservation, and material liquid is made;
(2) it after mixing polyvinyl alcohol and deionized water according to the ratio that mass ratio is 1: 8-12, is added into material liquid,
Addition is the 10-20% of material liquid quality, then the temperature of reaction system is risen to 80-85 DEG C, and reaction 1.5-2.5 is mixed
After hour, filtering obtains Archon;
(3) it is 1: 7: 0.4-0.5 according to mass ratio by Archon, the sulfuric acid that mass fraction is 90%, 1,2- dichloromethane
After ratio mixing, the temperature of mixture is risen to 95-100 DEG C, insulation reaction is after 3-4 hours, and filtering, filter residue, which is washed to pH, is
6.5-7.5 after, sulphur ball is made;
(4) sulphur ball made from step (3) is added into rare-earth salt solution, 35-40 DEG C of temperature after crossing 30-70 mesh sieve
Stirring dipping filters after 2-2.5 hours, washing, after dry, rare earth modified cation exchange resin is made, wherein rare-earth salts is molten
Liquid is made of the component of following parts by weight:4-8 parts of lanthanum chloride, 1-3 parts of europium nitrate, 160-170 parts of water;
(5) after mixing benzyl alcohol and glacial acetic acid according to the ratio that molar ratio is 1: 1.0-1.4, benzyl alcohol is added thereto
With the rare earth modified cation exchange resin of glacial acetic acid gross mass 28-32%, the hexamethylene of the 15-18% of benzyl alcohol quality mixes
After conjunction stirs evenly, it is heated to 85-90 DEG C, benzyl acetate is made after 4-5 hours in insulation reaction.
Specifically, in above-mentioned steps (1), when heat preservation is persistently stirred to react, the rotating speed of stirring is 350-400r/min.
Specifically, in above-mentioned steps (2), polyvinyl alcohol is 1788 type of polyvinyl alcohol, 1795 type of polyvinyl alcohol, polyvinyl alcohol
Any one in 1797 types.
Preferably, in above-mentioned steps (3), it is 6.5 to be washed to pH value.
From the above technical scheme, it can be seen that the beneficial effects of the invention are as follows:
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate provided by the invention, synthesis of acetic acid
The raw material of benzyl ester is benzyl alcohol, glacial acetic acid, and the two is liquid, and rare earth modified cation exchange resin is solid catalyst, instead
Should after be separated by solid-liquid separation conveniently, it is convenient that catalyst is recycled compared with the concentrated sulfuric acid catalyst of conventional method, and post-processing is simple and convenient, and
Environmentally protective, relatively low to equipment requirement, the esterification yield of benzyl acetate is up to 68.67% or so;Meanwhile rare earth produced by the present invention
Modified cation-exchange resin, high recycling rate are conducive to save production cost.
Description of the drawings
Fig. 1 is the infrared spectrogram of Archon obtained in 2 step of embodiment (2).
Fig. 2 is the infrared spectrogram of sulphur ball obtained in 2 step of embodiment (3).
Fig. 3 is the infrared spectrogram of rare earth modified cation exchange resin obtained in 2 step of embodiment (4).
Fig. 4 is the infrared spectrogram of benzyl acetate obtained in 2 step of embodiment (5).
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, including following operating procedure:
(1) 38 DEG C are heated to after mixing styrene and divinylbenzene according to the ratio that molar ratio is 7.14: 1, then to its
5min is persistently stirred in the middle initiator B PO that styrene quality 2.0% is added, heat preservation, and material liquid is made;
(2) it after mixing polyvinyl alcohol and deionized water according to the ratio that mass ratio is 1: 8, is added into material liquid, adds
Enter 10% that amount is material liquid quality, then the temperature of reaction system is risen to 80 DEG C, after reaction being mixed 1.5-2.5 hours,
Filtering, obtains Archon;
(3) ratio for being 1: 7: 0.4 according to mass ratio by Archon, the sulfuric acid that mass fraction is 90%, 1,2- dichloromethane
After mixing, the temperature of mixture is risen to 95 DEG C, insulation reaction is after 3 hours, filtering, and filter residue is washed to after pH is 6.0, is made
Sulphur ball;
(4) sulphur ball made from step (3) is added after crossing 30 mesh sieve into rare-earth salt solution, 35 DEG C of temperature stirring leaching
It after stain 2 hours, filters, washing, after dry, rare earth modified cation exchange resin is made, wherein rare-earth salt solution is by following heavy
The component of amount part is made:4 parts of lanthanum chloride, 1 part of europium nitrate, 160 parts of water;
(5) after mixing benzyl alcohol and glacial acetic acid according to the ratio that molar ratio is 1: 1.0, benzyl alcohol and ice are added thereto
The rare earth modified cation exchange resin of acetic acid gross mass 28%, 15% hexamethylene of benzyl alcohol quality, is mixed evenly
Afterwards, 85 DEG C are heated to, benzyl acetate is made after 4 hours in insulation reaction.
Specifically, in above-mentioned steps (1), when heat preservation is persistently stirred to react, the rotating speed of stirring is 350r/min.
Specifically, in above-mentioned steps (2), polyvinyl alcohol is 1788 type of polyvinyl alcohol.
In the present embodiment, esterification yield 68.02%.
Embodiment 2
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, including following operating procedure:
(1) 38 DEG C are heated to after mixing styrene and divinylbenzene according to the ratio that molar ratio is 7.14: 1, then to its
5min is persistently stirred in the middle initiator B PO that styrene quality 2.0% is added, heat preservation, and material liquid is made;
(2) it after mixing polyvinyl alcohol and deionized water according to the ratio that mass ratio is 1: 10, is added into material liquid, adds
Enter 15% that amount is material liquid quality, then the temperature of reaction system is risen to 83 DEG C, after reaction being mixed 2 hours, filtering obtains
To Archon;
(3) ratio for being 1: 7: 0.4 according to mass ratio by Archon, the sulfuric acid that mass fraction is 90%, 1,2- dichloromethane
After mixing, the temperature of mixture is risen to 98 DEG C, insulation reaction is after 3.5 hours, filtering, filter residue is washed to after pH is 6.5, system
Obtain sulphur ball;
(4) sulphur ball made from step (3) is added after crossing 50 mesh sieve into rare-earth salt solution, 38 DEG C of temperature stirring leaching
It after stain 2.3 hours, filters, washing, after dry, rare earth modified cation exchange resin is made, wherein rare-earth salt solution is by following
The component of parts by weight is made:6 parts of lanthanum chloride, 2 parts of europium nitrate, 165 parts of water;
(5) after mixing benzyl alcohol and glacial acetic acid according to the ratio that molar ratio is 1: 1.2, benzyl alcohol and ice are added thereto
The rare earth modified cation exchange resin of acetic acid gross mass 30%, the hexamethylene of the 15-18% of benzyl alcohol quality are mixed equal
After even, 88 DEG C are heated to, benzyl acetate is made after 4.5 hours in insulation reaction.
Specifically, in above-mentioned steps (1), when heat preservation is persistently stirred to react, the rotating speed of stirring is 380r/min.
Specifically, in above-mentioned steps (2), polyvinyl alcohol is 1795 type of polyvinyl alcohol.
In the present embodiment, esterification yield 69.10%.
Embodiment 3
A kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, including following operating procedure:
(1) 42 DEG C are heated to after mixing styrene and divinylbenzene according to the ratio that molar ratio is 7.14: 1, then to its
5-10min is persistently stirred in the middle initiator B PO that styrene quality 3.0% is added, heat preservation, and material liquid is made;
(2) it after mixing polyvinyl alcohol and deionized water according to the ratio that mass ratio is 1: 12, is added into material liquid, adds
Enter 20% that amount is material liquid quality, then the temperature of reaction system is risen to 85 DEG C, after reaction being mixed 2.5 hours, filtering,
Obtain Archon;
(3) ratio for being 1: 7: 0.5 according to mass ratio by Archon, the sulfuric acid that mass fraction is 90%, 1,2- dichloromethane
After mixing, the temperature of mixture is risen to 100 DEG C, insulation reaction is after 4 hours, filtering, filter residue is washed to after pH is 7.0, system
Obtain sulphur ball;
(4) sulphur ball made from step (3) is added after crossing 70 mesh sieve into rare-earth salt solution, 40 DEG C of temperature stirring leaching
It after stain 2.5 hours, filters, washing, after dry, rare earth modified cation exchange resin is made, wherein rare-earth salt solution is by following
The component of parts by weight is made:8 parts of lanthanum chloride, 3 parts of europium nitrate, 170 parts of water;
(5) after mixing benzyl alcohol and glacial acetic acid according to the ratio that molar ratio is 1: 1.4, benzyl alcohol and ice are added thereto
The rare earth modified cation exchange resin of acetic acid gross mass 32%, 18% hexamethylene of benzyl alcohol quality, is mixed evenly
Afterwards, 90 DEG C are heated to, benzyl acetate is made after 5 hours in insulation reaction.
Specifically, in above-mentioned steps (1), when heat preservation is persistently stirred to react, the rotating speed of stirring is 400r/min.
Specifically, in above-mentioned steps (2), polyvinyl alcohol is 1797 type of polyvinyl alcohol.
In the present embodiment, esterification yield 68.72%.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (4)
1. a kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate, which is characterized in that including following behaviour
Make step:
(1) after mixing styrene and divinylbenzene according to the ratio that molar ratio is 7.14: 1, be heated to 38-42 DEG C, then to its
5-10min is persistently stirred in the middle initiator B PO that styrene quality 2.0-3.0% is added, heat preservation, and material liquid is made;
(2) it after mixing polyvinyl alcohol and deionized water according to the ratio that mass ratio is 1: 8-12, is added into material liquid, is added
Amount is the 10-20% of material liquid quality, then the temperature of reaction system is risen to 80-85 DEG C, and reaction 1.5-2.5 hours is mixed
Afterwards, it filters, obtains Archon;
(3) ratio for being 1: 7: 0.4-0.5 according to mass ratio by Archon, the sulfuric acid that mass fraction is 90%, 1,2- dichloromethane
After mixing, the temperature of mixture is risen to 95-100 DEG C, insulation reaction is after 3-4 hours, filtering, and it is 6.0- that filter residue, which is washed to pH,
After 7.0, sulphur ball is made;
(4) sulphur ball made from step (3) is added after crossing 30-70 mesh sieve into rare-earth salt solution, 35-40 DEG C of temperature stirring
Dipping filters after 2-2.5 hour, washing, after dry, obtained rare earth modified cation exchange resin, wherein rare-earth salt solution by
The component of following parts by weight is made:4-8 parts of lanthanum chloride, 1-3 parts of europium nitrate, 160-170 parts of water;
(5) after mixing benzyl alcohol and glacial acetic acid according to the ratio that molar ratio is 1: 1.0-1.4, benzyl alcohol and ice are added thereto
The rare earth modified cation exchange resin of acetic acid gross mass 28-32%, the hexamethylene of the 15-18% of benzyl alcohol quality, mixing are stirred
After mixing uniformly, it is heated to 85-90 DEG C, benzyl acetate is made after 4-5 hours in insulation reaction.
2. a kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate according to claim 1,
It is characterized in that, in above-mentioned steps (1), when heat preservation is persistently stirred to react, the rotating speed of stirring is 350-400r/min.
3. a kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate according to claim 1,
It is characterized in that, in above-mentioned steps (2), polyvinyl alcohol is 1788 type of polyvinyl alcohol, 1795 type of polyvinyl alcohol, 1797 type of polyvinyl alcohol
In any one.
4. a kind of method of rare earth modified catalyzing cation exchange resin synthetic benzyl acetate according to claim 1,
It is characterized in that, it is preferable that in above-mentioned steps (3), it is 6.5 to be washed to pH value.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101445573A (en) * | 2007-11-27 | 2009-06-03 | 上海交通大学 | Method for preparing single-dispersibility polystyrene-DVE |
CN101735372A (en) * | 2009-12-28 | 2010-06-16 | 西安蓝晓科技有限公司 | Novel chelate resin and production method and application thereof |
CN104402719A (en) * | 2014-12-01 | 2015-03-11 | 福州福大辉翔化工科技有限公司 | Preparation method of benzyl acetate |
CN104525260A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Polymeric solid acid catalyst for esterification reaction and preparation method thereof |
CN105037783A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for rare earth modified strongly acidic styrene cation exchange resin |
-
2018
- 2018-04-13 CN CN201810382259.5A patent/CN108558660A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101445573A (en) * | 2007-11-27 | 2009-06-03 | 上海交通大学 | Method for preparing single-dispersibility polystyrene-DVE |
CN101735372A (en) * | 2009-12-28 | 2010-06-16 | 西安蓝晓科技有限公司 | Novel chelate resin and production method and application thereof |
CN104402719A (en) * | 2014-12-01 | 2015-03-11 | 福州福大辉翔化工科技有限公司 | Preparation method of benzyl acetate |
CN104525260A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Polymeric solid acid catalyst for esterification reaction and preparation method thereof |
CN105037783A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for rare earth modified strongly acidic styrene cation exchange resin |
Non-Patent Citations (4)
Title |
---|
朱万仁: "乙酸正丁酯的催化酯化研究 ", 《玉林师专学报》 * |
甘黎明: "以阳离子交换树脂负载镧作催化剂合成乙酸异戊酯 ", 《内蒙古石油化工》 * |
蒋红芝等: "乙酸苄酯合成过程强化实验及产物分析研究", 《应用化工》 * |
顾觉奋等: "《离子交换与吸附树脂在制药工业上的应用》", 30 April 2008, 中国医药科技出版社 * |
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