CN109535104B - A kind of production method of epoxidized soybean oil - Google Patents
A kind of production method of epoxidized soybean oil Download PDFInfo
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- CN109535104B CN109535104B CN201811376593.6A CN201811376593A CN109535104B CN 109535104 B CN109535104 B CN 109535104B CN 201811376593 A CN201811376593 A CN 201811376593A CN 109535104 B CN109535104 B CN 109535104B
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- soybean oil
- epoxidized soybean
- formic acid
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- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
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Abstract
The invention discloses a kind of production methods of epoxidized soybean oil, using two-step synthesis, comprising the following steps: (1) hydrogen peroxide, formic acid and catalyst are added in autoclave, stirring, cooling obtain peroxidating formic acid;(2) soybean oil is added dropwise in the peroxidating formic acid obtained to step (1), is passed through oxygen, stirring, compressive reaction obtain epoxidized soybean oil crude product;(3) epoxidized soybean oil crude product progress alkali cleaning, washing, vacuum distillation that step (2) obtains are obtained into epoxidized soybean oil finished product.Compared with prior art, cost of the invention is low, reaction temperature controllability is good, reaction speed is fast, and by-product is few, the good product quality of acquisition.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical fields, and in particular to a kind of production method of epoxidized soybean oil.
Background technique
Epoxidized soybean oil is to have increasing concurrently using nontoxic non-benzene class environment-friendly type plastic auxiliary agent-plasticizer widely at present
Modeling and heat-staple dual property, and nontoxic, safety and environmental protection, therefore the favor by plastic article industry in plastics, apply
Have in the industrial circles such as material, novel high polymer material, rubber and widely applies.With the raising of countries in the world environmental consciousness, increase
The toxicity of modeling agent has been to be concerned by more and more people;Plasticizer phthalic acid ester class product is many flourishing because there is carcinogenic suspicion
Country has forbidden it to use in the plastic products such as medical treatment and food packaging, daily necessities, toy.And since oil supply is inclined
Tightly, international, state's reactive plasticizer market price skyrockets, and the raw material that epoxidized soybean oil and epoxyfatty acid mainly utilize is renewable
Resource, product have a vast market foreground.
Soybean oil process for epoxidation mainly has solvent method and solventless method: (1) solvent method was needed using benzene, toluene, heptan
A large amount of organic solvents such as alkane, hexane, chloroform, pollute the environment, and the production equipment needed is more, and three-protection design amount is big, raw
The epoxidized soybean oil epoxide number that output is come is low, and poor product quality is gradually eliminated substantially.(2) solventless method is mainly with first
As active oxygen carrier, it is anti-to carry out epoxidation under the action of catalyst for donor of the 27-50% hydrogen peroxide as oxygen for acid or acetic acid
It answers, epoxy agent is added drop-wise in soybean oil in a certain temperature range, common catalyst has sulfuric acid, highly acidic cation exchange
Resin, furthermore there are also solid acids (such as aluminum sulfate, ferric sulfate), heteropoly acid, solid super strong for the catalyst of synthesizing epoxy soybean oil
Acid, molecular sieve etc. remove water through alkali cleaning, washing, vacuum distillation after epoxidation reaction, finally obtain product.Reaction process is short, reaction
Temperature is low, and the reaction time is short, and by-product is few, and product epoxide number is high, lighter color, good product quality, produces easy to control, operation letter
Just.
CN86104989A discloses a kind of production method of epoxidized soybean oil, this method soybean oil, 39% hydrogen peroxide,
The concentrated sulfuric acid, glacial acetic acid react 7~8 hours, one-step synthesis product epoxidized soybean oil, and epoxide number is generated in 6.0-6.4, this method
The easy open loop of epoxy group, especially in the epoxidation later period, since oxidant hydrogen peroxide concentration reduces, epoxidation speed is slower, production
Period is long, and reaction temperature is not easy to control.
CN102061222A discloses a kind of continuous producing method of epoxidized soybean oil, using soybean oil as raw material, is added dropwise
Hydrogen peroxide, formic acid and the concentrated sulfuric acid are carried out continuously epoxidation processing in the reaction kettle that three are connected in series, obtain epoxy after purification
Soybean oil, the epoxide number of obtained epoxidized soybean oil finished product are 6.15-6.4, iodine number 2-4.Wherein, it is connected in series at epoxidation
Specific step is as follows for reason: soybean oil, hydrogen peroxide, formic acid and the concentrated sulfuric acid (1) are added to the first reaction of series connection according to the ratio
It is stirred continuously in kettle, under the conditions of 60-80 DEG C, reacts 2.5-4.0 hours, divide except water layer obtains epoxidised soybean oil A;(2) will
Epoxidised soybean oil A, hydrogen peroxide, formic acid and the concentrated sulfuric acid in mass ratio 1: 0.84-0.90: 0.03-0.10: 0.004-
0.006 is added in the second reaction kettle and is stirred continuously, and wherein the concentration of hydrogen peroxide is 23-26%, under the conditions of 70-80 DEG C, reaction
2-3.5 hours, divide except water layer obtains epoxidised soybean oil B;(3) epoxidised soybean oil B, hydrogen peroxide, formic acid and the concentrated sulfuric acid are pressed
Quality proportioning is 1: 0.5-0.9: 0.04-0.10: 0.003-0.006 to be added in third reaction kettle and be stirred continuously, wherein hydrogen peroxide
Concentration be 50%, under the conditions of 65-75 DEG C, react 2-3.5 hour, point remove water layer obtain epoxidized soybean oil crude product;The invention
Water consumption it is big, subsequent cost of sewage disposal is high, and epoxidation temperatures are higher, and epoxidation speed is fast, is conducive to epoxidation reaction
It is carried out to target product, but high temperature can accelerate the generation of the side reactions such as hydrolysis simultaneously, influence the quality of product.
Currently, non-solvent method synthesizing epoxy soybean oil is there are still product epoxide number, low (the epoxide number bottleneck of domestic industry is
6.5g/100gESO), by-product is more, and post-processing is relative complex, reaction temperature is higher, the reaction time is longer and the cost of catalyst
The problems such as high.Therefore, it needs to improve the production method of epoxidized soybean oil in the prior art.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of production method of epoxidized soybean oil, the production
Method and process is simple, at low cost, reaction temperature controllability is good, reaction speed is fast, and by-product is few, the good product quality of acquisition.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of production method of epoxidized soybean oil, using two-step synthesis, comprising the following steps:
(1) hydrogen peroxide, formic acid and catalyst are added in autoclave, stirring, cooling obtain peroxidating formic acid;
(2) soybean oil is added dropwise in the peroxidating formic acid obtained to step (1), is passed through oxygen, stirring, compressive reaction obtain
Epoxidized soybean oil crude product;
(3) epoxidized soybean oil crude product progress alkali cleaning, washing, vacuum distillation that step (2) obtains are obtained into epoxidized soybean oil
Finished product.
Preferably, the mass ratio of hydrogen peroxide, formic acid and catalyst described in step (1) is 1:(0.03-0.10):
(0.003-0.009)。
It is further preferred that the concentration of the hydrogen peroxide is 55-65%.
Preferably, cooling temperature described in step (1) is 50-65 DEG C.
Preferably, catalyst described in step (1) is the mixture of phosphorus heteropoly tungstic acid and manganese benzoate.
Further preferably, the mass ratio 1:(2-5 of the phosphorus heteropoly tungstic acid and manganese benzoate).
Preferably, the mass ratio of soybean oil described in step (2) and hydrogen peroxide described in step (1) is (1.2-
1.8): 1.
Preferably, soybean oil described in step (2) all drips off in 0.5-1h.
Preferably, the revolving speed of stirring described in step (1) and step (2) is 200-450rpm.
Preferably, in step (2) compressive reaction condition are as follows: pressure 0.9-1.5Mpa, reaction time 1-2h;Into one
Walking preferred pressure is 1.0-1.5Mpa, reaction time 1.2-1.5h.
Preferably, the intake of oxygen described in step (2) is 10-50L;Further preferably 15-45L.
Meanwhile the present invention also provides epoxidized soybean oils made from aforementioned production method.
Compared with prior art, the invention has the benefit that
(1) present invention is big using phosphorus heteropoly tungstic acid and manganese benzoate as catalyst preparation epoxy using hydrogen peroxide as oxygen source
Soya-bean oil is used as catalyst without using strong acid in reaction system of the invention, corrodes to equipment and corrosive pipeline is small, used catalyst
Dosage is small, and reactivity is high, and at low cost, byproduct of reaction is few, and product postprocessing is simple, is not required to be deacidified with massive laundering, reduces
Sewage treatment burden.
(2) soybean oil is added dropwise in peroxidating formic acid by the present invention in synthetic system, reduces reaction volume, temperature can
Control property is good, reduces production cost, while being passed through oxygen in whipping process, can effectively reduce the generation of byproduct of reaction,
Improve the quality of epoxidized soybean oil.
(3) production method of the epoxidized soybean oil is reasonable, is able to achieve Precise control, higher to the removal rate of impurity, and
And can be improved the product quality of epoxidized soybean oil, reduce work hours, reduce reaction volume, reduce production cost, improves production effect
Rate reduces sewage yield, saves subsequent sewage treatment burden, can generate preferable economic benefit and social benefit.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment;It is also understood that term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than limiting the scope of protection of the present invention.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, all technologies used herein and section
Technics has and the normally understood identical meaning of general technical staff of the technical field of the invention.
The present invention is not defined the source of raw material, and all raw materials used in the present embodiment are common commercially available production
Product.
Embodiment 1
(1) taking concentration is 55% hydrogen peroxide 100g, 3g formic acid, 0.1g phosphorus heteropoly tungstic acid and 0.2g manganese benzoate, successively
It is added in autoclave, 2h is stirred with the revolving speed of 200rpm, 50 DEG C is cooled to, obtains peroxidating formic acid mixtures;
(2) in the peroxidating formic acid mixtures obtained to step (1), 120g soybean oil is slowly added dropwise, controls soybean oil
Flow velocity drips off it all in 0.8h;During dropwise addition, it is passed through 10L oxygen, control mixing speed is 200rpm, and temperature is
60 DEG C, pressure 0.9Mpa, 2h is reacted, epoxidized soybean oil crude product is obtained;
(3) the epoxidized soybean oil crude product for obtaining step (2) carries out alkali cleaning, washing, decompression steaming according to conventional technical means
It evaporates to obtain epoxidized soybean oil finished product.
Embodiment 2
(1) taking concentration is 65% hydrogen peroxide 100g, 10g formic acid, 0.3g phosphorus heteropoly tungstic acid and 0.6g manganese benzoate, successively
It is added in autoclave, 1h is stirred with the revolving speed of 450rpm, 60 DEG C is cooled to, obtains peroxidating formic acid mixtures;
(2) in the peroxidating formic acid mixtures obtained to step (1), 180g soybean oil is slowly added dropwise, controls soybean oil
Flow velocity drips off it all in 1h;During dropwise addition, it is passed through 50L oxygen, control mixing speed is 450rpm, temperature 60
DEG C, pressure 1.2Mpa reacts 1h, obtains epoxidized soybean oil crude product;
(3) the epoxidized soybean oil crude product for obtaining step (2) carries out alkali cleaning, washing, decompression steaming according to conventional technical means
It evaporates to obtain epoxidized soybean oil finished product.
Embodiment 3
(1) taking concentration is 60% hydrogen peroxide 100g, 8g formic acid, 0.05g phosphorus heteropoly tungstic acid and 0.25g manganese benzoate, according to
It is secondary to be added in autoclave, 1h is stirred with the revolving speed of 300rpm, 55 DEG C is cooled to, obtains peroxidating formic acid mixtures;
(2) in the peroxidating formic acid mixtures obtained to step (1), 160g soybean oil is slowly added dropwise, controls soybean oil
Flow velocity drips off it all in 0.5h;During dropwise addition, it is passed through 15L oxygen, control mixing speed is 450rpm, and temperature is
60 DEG C, pressure 1.0Mpa, 1.5h is reacted, epoxidized soybean oil crude product is obtained;
(3) the epoxidized soybean oil crude product for obtaining step (2) carries out alkali cleaning, washing, decompression steaming according to conventional technical means
It evaporates to obtain epoxidized soybean oil finished product.
Embodiment 4
(1) taking concentration is 63% hydrogen peroxide 100g, 5g formic acid, 0.15g phosphorus heteropoly tungstic acid and 0.75g manganese benzoate, according to
It is secondary to be added in autoclave, 1h is stirred with the revolving speed of 450rpm, 65 DEG C is cooled to, obtains peroxidating formic acid mixtures;
(2) in the peroxidating formic acid mixtures obtained to step (1), 140g soybean oil is slowly added dropwise, controls soybean oil
Flow velocity drips off it all in 0.7h;During dropwise addition, it is passed through 45L oxygen, control mixing speed is 200rpm, and temperature is
60 DEG C, pressure 1.5Mpa, 1.2h is reacted, epoxidized soybean oil crude product is obtained;
(3) the epoxidized soybean oil crude product for obtaining step (2) carries out alkali cleaning, washing, decompression steaming according to conventional technical means
It evaporates to obtain epoxidized soybean oil finished product.
Comparative example 1
The present embodiment difference from example 1 is that, the concentration of the hydrogen peroxide is 50%, soybean oil 100g.
Comparative example 2
The present embodiment and embodiment 2 the difference is that, the concentration of the hydrogen peroxide is 70%, soybean oil 200g.
Comparative example 3
The present embodiment and embodiment 3 the difference is that, the phosphorus heteropoly tungstic acid is 0.3g, and the manganese benzoate is
0.1g。
Comparative example 4
The present embodiment and embodiment 3 the difference is that, the phosphorus heteropoly tungstic acid is 0.05g, and the manganese benzoate is
0.8g。
Comparative example 5
The present embodiment and embodiment 4 the difference is that, obstructed oxygen.
Comparative example 6
The present embodiment and embodiment 4 the difference is that, the amount for being passed through oxygen is 8L, reaction pressure 2.0Mpa, instead
It is 1.5h between seasonable.
The quality determination of the epoxidized soybean oil produced by the invention of table 1
In addition, the present invention is using hydrogen peroxide as oxygen source, using phosphorus heteropoly tungstic acid and manganese benzoate as catalyst preparation epoxy
Soybean oil is used as catalyst without using strong acid in reaction system of the invention, corrodes to equipment and corrosive pipeline is small, catalysis used
Agent dosage is small, and reactivity is high, and at low cost, byproduct of reaction is few, and product postprocessing is simple, does not have to massive laundering and deacidifies, can be with
The sewage discharge for reducing 20-30%, is effectively reduced environmental pollution.
Claims (5)
1. a kind of production method of epoxidized soybean oil, which is characterized in that use two-step synthesis, comprising the following steps:
(1) hydrogen peroxide, formic acid and catalyst are added in autoclave, stirring, cooling obtain peroxidating formic acid;
Catalyst as described in step (1) is the mixture of phosphorus heteropoly tungstic acid and manganese benzoate;The phosphorus heteropoly tungstic acid and benzene
The mass ratio 1:(2-5 of formic acid manganese);
(2) soybean oil is added dropwise in the peroxidating formic acid obtained to step (1), is passed through oxygen, stirring, compressive reaction, obtains epoxy
Soybean oil crude product;
Soybean oil described in step (2) all drips off in 0.5-1h;
The intake of oxygen described in step (2) is 10-50L;
(3) epoxidized soybean oil crude product progress alkali cleaning, washing, vacuum distillation that step (2) obtain are obtained into epoxidized soybean oil finished product.
2. production method according to claim 1, which is characterized in that hydrogen peroxide, formic acid and catalysis as described in step (1)
The mass ratio of agent is 1:(0.03-0.10): (0.003-0.009).
3. production method according to claim 1, which is characterized in that in soybean oil described in step (2) and step (1)
The mass ratio of the hydrogen peroxide is (1.2-1.8): 1.
4. production method according to claim 1, which is characterized in that stirring described in step (1) and step (2) turns
Speed is 200-450rpm.
5. production method according to claim 1, which is characterized in that the condition of compressive reaction described in step (2) are as follows: pressure
Power is 0.9-1.5Mpa, reaction time 1-2h.
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环氧大豆油合成实验研究;王燕石;《河北化工》;20080229;第31卷(第2期);第37-38页 |
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Denomination of invention: A production method of epoxy soybean oil Effective date of registration: 20220519 Granted publication date: 20190830 Pledgee: Agricultural Bank of China Limited Qingyuan Qingxin sub branch Pledgor: HONGLIDA (GUANGDONG) SYNTHESIS MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2022980005942 |
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