CN105924328B - A kind of highly selective green hydrolysis technique for preparing benzyl alcohol - Google Patents
A kind of highly selective green hydrolysis technique for preparing benzyl alcohol Download PDFInfo
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- CN105924328B CN105924328B CN201610332148.4A CN201610332148A CN105924328B CN 105924328 B CN105924328 B CN 105924328B CN 201610332148 A CN201610332148 A CN 201610332148A CN 105924328 B CN105924328 B CN 105924328B
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- reaction
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- benzyl
- benzyl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
Abstract
The invention discloses a kind of highly selective green hydrolysis techniques for preparing benzyl alcohol, it the steps include: according to 1.05~1.1:1:7.0:0.02 of molar ratio to put into sodium formate, benzyl chloride, water and Tertiary organic amine catalysts in reactor, it is sufficiently mixed stirring, first 8 ~ 9h of synthesis under normal pressure at 100 ~ 115 DEG C, stop heating, reduce the temperature to 95 ~ 105 DEG C, the caustic soda of investment and benzyl chloride equimolar amounts the reaction was continued 2 ~ 3h；The mixed material of reaction is filtered, and removes solid sodium chloride, and liquid phase is cooling, separates organic phase；Organic phase is separated by rectifying and high-purity benzene methanol is made；Water phase returns reactor, carries out the reaction of recirculated water solution after adding each raw material.The present invention uses sodium formate for auxiliary agent, and trimethylamine is that catalyst is hydrolyzed benzyl chloride and prepares benzyl alcohol, and the Tertiary organic amine catalysts of use are cheap, high catalytic efficiency；The water phase of reaction can recycle, and solve the problems, such as the high-salt wastewater of benzyl alcohol production process, while greatly reduce the content of benzyl ether, and dibenzyl ether content is below 3.5%.
Description
Technical field
The present invention relates to organic chemical industries to synthesize field, and in particular to a kind of highly selective green hydrolysis work for preparing benzyl alcohol
Skill.
Background technique
Currently, the production method of benzyl alcohol mainly uses benzyl chloride level-one normal pressure alkaline hydrolysis and high pressure second level to hydrolyze, high pressure two
Grade hydrolysis divides alkaline hydrolysis and without basic hydrolysis again.The main problem that existing ordinary-pressure hydrolysis faces is that technique generates a large amount of high-salt wastewater
With by-product benzyl ether, processing cost is higher；High pressure alkaline hydrolysis equally faces the problem of high-salt wastewater, and high pressure is faced without basic hydrolysis
A large amount of waste hydrochloric acid needs to handle；Highly pressured hydrolysis is higher to the requirement of equipment simultaneously.In addition existing process equipment uses
Rate is lower, and concentration of lye is lower, and 8 ~ 13% or so, and the water that alkali-free hydrolysis process uses is larger, up to the 5 of benzyl chloride times
Quality.
Wastewater treatment is that one of maximum environmental problem, the processing of high-salt wastewater and spent acid bring huge to enterprise now
Cost pressure and environmental protection pressure, correlation processing technique also become puzzlement enterprise development problem.
Summary of the invention
The present invention in order to overcome the drawbacks of the prior art, proposes a kind of highly selective green hydrolysis work for preparing benzyl alcohol
Skill.The technological reaction selectivity is high, and by-product yields are reduced to 3.5% or less；Utilization rate of equipment and installations is high, and no high-salt wastewater generates,
The water phase that reaction process may be implemented recycles completely.
The present invention in order to solve the above technical problems, takes following technical scheme；It is a kind of highly selective to prepare the green of benzyl alcohol
Color hydrolysis process, the processing step are as follows:
(1) sodium formate, benzyl chloride, water and Tertiary organic amine catalysts are thrown according to 1.05~1.1:1:7.0:0.02 of molar ratio
Enter into reactor, is sufficiently mixed stirring, first 8 ~ 9h of synthesis under normal pressure at 100 ~ 115 DEG C, stops heating, reduce the temperature to 95 ~
105 DEG C, investment and the caustic soda of benzyl chloride equimolar amounts the reaction was continued 2 ~ 3h；
(2) mixed material reacted is filtered, and removes solid sodium chloride, and liquid phase is cooling, separates organic phase；
(3) organic phase is separated by rectifying and high-purity benzene methanol is made；
(4) water phase returns reactor, carries out the reaction of recirculated water solution after adding each raw material.
Further, in step (1) and (4), the purity of the sodium formate is 96%, and the purity of caustic soda is 98%, benzyl chloride
Purity >=99%, purity >=99% of Tertiary organic amine catalysts.
Further, in step (1), Tertiary organic amine catalysts molecular formula is, wherein R1, R2, R3 are 1 ~ 4
The alkyl of carbon.
Further, in step (1), first the synthesis under normal pressure 8h at 110 ~ 112 DEG C, reduces the temperature to 100 ~ 102 DEG C, continues
React 2.5 ~ 3h.
Further, in step (1), the water and sodium formate mass ratio are 1.3 ~ 1.1 times.
Further, in step (1), the preferred triethylamine of the Tertiary organic amine catalysts.
Compared with prior art, present invention has an advantage that
1, reaction system emits no waste water, and water phase is sodium chloride saturated solution, contains auxiliary agent sodium formate simultaneously.It can be real
Existing water phase recycles, and the sodium chloride for reacting formation is directly precipitated in solid form, convenient for processing.Avoid high-salt wastewater
Processing, greatly reduces production cost.
2, the conversion ratio of reaction process benzyl chloride is 99.9% or more, by-product benzyl ether accounting < 3.5%.The process choice
Property it is high, low for equipment requirements, utilization rate of equipment and installations is high, very good solution the deficiencies in the prior art.
Specific embodiment
Below in conjunction with specific embodiment, present invention is further described in detail, but the invention is not limited to the realities
Apply example.
The highly selective green hydrolysis technique for preparing benzyl alcohol of the present invention, the processing step are as follows:
(1) sodium formate, benzyl chloride, water and Tertiary organic amine catalysts are thrown according to 1.05~1.1:1:7.0:0.02 of molar ratio
Enter into reactor, is sufficiently mixed stirring, first 8 ~ 9h of synthesis under normal pressure at 100 ~ 115 DEG C, stops heating, reduce the temperature to 95 ~
105 DEG C, investment and the caustic soda of benzyl chloride equimolar amounts the reaction was continued 2 ~ 3h；
(2) mixed material reacted is filtered, and removes solid sodium chloride, and liquid phase is cooling, separates organic phase；
(3) organic phase is separated by rectifying and high-purity benzene methanol is made；
(4) water phase returns reactor, add 3% sodium formate, 2% water, 2% Tertiary organic amine catalysts, circulation hydrolysis
It applies.
Embodiment 1: the triethylamine of the sodium formate of 3.77kg, the water of 4.35kg, the benzyl chloride of 4.4kg and 0.071kg are added
Enter into the reaction kettle equipped with heating, stirring, thermometer and condenser pipe, opens and stir and heat, when kettle temperature is raised to 110 DEG C of beginnings
Temperature is set to 100 DEG C after reacting 8h by timing, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase
Composition are as follows: contain benzyl alcohol 95.66%, contain benzyl ether 2.83%.
Embodiment 2: by the N- butyl two of the sodium formate of 3.77kg, the water of 4.35kg, the benzyl chloride of 4.4kg and 0.071kg
Methylamine is added in the reaction kettle equipped with heating, stirring, thermometer and condenser pipe, is opened and is stirred and heat, when kettle temperature is raised to 110
DEG C start timing, after reacting 8h, temperature is set to 100 DEG C, puts into after the sodium hydroxide hydrolysis 3h of 1.36kg and sample point
Analysis, oily phase composition are as follows: contain benzyl alcohol 95.71%, contain benzyl ether 1.49%.
Embodiment 3: by the sodium formate of 3.77kg, the water of 4.35kg, the benzyl chloride of 4.4kg and 0.062kg N, N- diethyl
Base methylamine is added in the reaction kettle equipped with heating, stirring, thermometer and condenser pipe, is opened and is stirred and heat, when kettle temperature is raised to
Temperature is set to 100 DEG C after reacting 8h by 110 DEG C of beginning timing, puts into sampling after the sodium hydroxide hydrolysis 3h of 1.36kg
Analysis, oily phase composition are as follows: contain benzyl alcohol 96.11%, contain benzyl ether 2.14%.
Embodiment 4: the tripropyl amine (TPA) of the sodium formate of 3.77kg, the water of 4.35kg, the benzyl chloride of 4.4kg and 0.101kg are added
Enter into the reaction kettle equipped with heating, stirring, thermometer and condenser pipe, opens and stir and heat, when kettle temperature is raised to 110 DEG C of beginnings
Temperature is set to 100 DEG C after reacting 8h by timing, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase
Composition are as follows: contain benzyl alcohol 95.80%, contain benzyl ether 1.53%.
In order to verify effect of the invention, recycling for water phase is realized, inventor covers the water phase in embodiment 1
Use
Apply 1, add 0.188kg(5%) sodium formate, 0.09kg(2%) water, the triethylamine of 0.071kg is added, throw
The benzyl chloride of 4.4kg is opened into reaction kettle and stirs and heat,, will after reacting 8h when kettle temperature is raised to 110 DEG C of beginning timing
Temperature is set to 100 DEG C, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase composition are as follows: contains benzyl alcohol
94.51%, contain benzyl ether 3.21%.
Apply 2, add 0.188kg(5%) sodium formate, 0.09kg(2%) water, the triethylamine of 0.071kg is added, throw
The benzyl chloride of 4.4kg is opened into reaction kettle and stirs and heat,, will after reacting 8h when kettle temperature is raised to 110 DEG C of beginning timing
Temperature is set to 100 DEG C, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase composition are as follows: contains benzyl alcohol
96.71%, contain benzyl ether 2.69%.
Apply 3, add 0.188kg(5%) sodium formate, 0.09kg(2%) water, the triethylamine of 0.071kg is added, throw
The benzyl chloride of 4.4kg is opened into reaction kettle and stirs and heat,, will after reacting 8h when kettle temperature is raised to 110 DEG C of beginning timing
Temperature is set to 100 DEG C, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase composition are as follows: contains benzyl alcohol
96.41%, contain benzyl ether 2.87%.
Apply 4, add 0.188kg(5%) sodium formate, 0.09kg(2%) water, the triethylamine of 0.071kg is added, throw
The benzyl chloride of 4.4kg is opened into reaction kettle and stirs and heat,, will after reacting 8h when kettle temperature is raised to 110 DEG C of beginning timing
Temperature is set to 100 DEG C, puts into sampling analysis after the sodium hydroxide hydrolysis 3h of 1.36kg, oily phase composition are as follows: contains benzyl alcohol
96.82%, contain benzyl ether 2.42%.
It above embodiments and applies, benzyl chloride, triethylamine, sodium formate, sodium hydroxide are technical grade, and water is industrial
Water.Organic facies analysis result is by gas Chromatographic Determination.
By embodiment 1,2,3,4 with apply 1,2,3,4 comparisons: benzyl chloride conversion ratio of the invention, selectivity, production are imitated
Rate is all very high, has huge industrial application value.In addition, inventor through it is excessive the study found that reaction process formic acid
Sodium loss is since formic acid generation leads to partial loss, this part can be absorbed by lye and circulation adds realization.Tertiary amine
Catalyst is finally precipitated in benzyl ether in the form of quaternary ammonium salt, can be recycled by simple process.
Claims (5)
1. a kind of green hydrolysis technique for preparing benzyl alcohol, which is characterized in that the processing step is as follows:
(1) sodium formate, benzyl chloride, water and Tertiary organic amine catalysts are put into according to 1.05~1.1:1:7.0:0.02 of molar ratio
In reactor, it is sufficiently mixed stirring, first 8 ~ 9h of synthesis under normal pressure at 100 ~ 115 DEG C, stops heating, reduce the temperature to 95 ~ 105
DEG C, investment and the caustic soda of benzyl chloride equimolar amounts the reaction was continued 2 ~ 3h, wherein Tertiary organic amine catalysts molecular formula is, wherein R1, R2, R3 are the alkyl of 1 ~ 4 carbon；
(2) mixed material reacted is filtered, and removes solid sodium chloride, and liquid phase is cooling, separates organic phase；
(3) organic phase is separated by rectifying and high-purity benzene methanol is made；
(4) water phase returns reactor, carries out the reaction of recirculated water solution after adding each raw material.
2. hydrolysis process as described in claim 1, which is characterized in that in step (1) and (4), the sodium formate purity is
96%, caustic soda purity is 98%, benzyl chloride purity >=99%, Tertiary organic amine catalysts purity >=99%.
3. hydrolysis process as described in claim 1, which is characterized in that in step (1), the Tertiary organic amine catalysts are three
Ethamine.
4. hydrolysis process as described in claim 1, which is characterized in that in step (1), the first synthesis under normal pressure at 110 ~ 112 DEG C
8h reduces the temperature to 100 ~ 102 DEG C, the reaction was continued 2.5 ~ 3h.
5. hydrolysis process as described in claim 1, which is characterized in that in step (1), the water is with sodium formate mass ratio
1.3 ~ 1.1 times.
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| CN108821948B (en) * | 2018-08-22 | 2021-09-10 | 武汉有机实业有限公司 | Method for recycling benzyl alcohol rectification by-product |
| CN110776398B (en) * | 2019-11-08 | 2024-03-22 | 鲁西化工集团股份有限公司氯碱化工分公司 | Benzyl alcohol step pressurizing hydrolysis reaction process and system |
| CN115536492B (en) * | 2022-09-29 | 2023-12-19 | 潜江新亿宏有机化工有限公司 | Benzyl alcohol production method and device for reducing sodium carbonate consumption |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757312A (en) * | 2012-07-27 | 2012-10-31 | 湖北绿色家园精细化工有限责任公司 | High-selectivity and low-energy-consumption preparation method for benzyl alcohol |
| CN104926611A (en) * | 2015-05-31 | 2015-09-23 | 湖北绿色家园精细化工股份有限公司 | Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1064265A (en) * | 1991-02-11 | 1992-09-09 | 大连大学工学院 | The technology of synthesizing benzyl acelate by phase transfering catalysis |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757312A (en) * | 2012-07-27 | 2012-10-31 | 湖北绿色家园精细化工有限责任公司 | High-selectivity and low-energy-consumption preparation method for benzyl alcohol |
| CN104926611A (en) * | 2015-05-31 | 2015-09-23 | 湖北绿色家园精细化工股份有限公司 | Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride |
Non-Patent Citations (3)
| Title |
|---|
| 氯化苄经苯甲酸苄酯水解制备苯甲醇研究;张珍明等;《化工时刊》;20060606;第20卷(第6期);第49-51页 |
| 相转移催化法合成乙酸苄酯;童兴龙;《现代化工》;19931231(第6期);第24-25页 |
| 高收率苯 甲醇制备工艺研究;李树安;《化学工程师》;19991231;第3卷(第72期);第11-12页 |
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