CN102503912B - High epoxide number environment-friendly plasticizer production process - Google Patents
High epoxide number environment-friendly plasticizer production process Download PDFInfo
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Abstract
The invention discloses a high epoxide number environment-friendly plasticizer production process. The production process comprises the following steps of: adding cottonseed oil, methanol and sodium methoxide into an ester exchange reactor for reaction to obtain mixed fatty acid methyl ester; adding into a rectifying tower for separation, and performing epoxidation, neutralization, washing and dehydration on methyl oleate obtained from the tower bottom to obtain a high epoxide number environment-friendly plasticizer; and performing sulfonation reaction on palmitic acid methyl ester obtained from the tower top and sulfur trioxide, and ageing, esterifying, neutralizing and drying to obtain an environment-friendly surfactant MES. By the production process, the raw materials are readily available, the process is advanced, equipment is simple, the high epoxide number plasticizer can be prepared, and the byproduct, namely the palmitic acid methyl ester can be used for producing the environment-friendly surfactant.
Description
Technical field
The present invention relates to a kind of high epoxy value environment-friendly type plasticizer production process, belong to chemical field.
Background technology
Along with the whole world strengthens environmental protection consciousness, additives for plastics has been proposed to higher hygienic requirements, in recent years the new Application Areas of plant oil based softening agent and new oxidation technology (containing two keys) are become to study hotspot.Output sustainable growth in recent years, the consumption of epoxy plasticizer have accounted for softening agent total amount 9-10%, and its consumption is only second to phthalic ester and fatty group dibasic acid in the U.S., account for the 3rd of consumption.At present, the principal item of industrial epoxidized plasticizer comprises: epoxidised soybean oil, epoxidation Oleum Gossypii semen, epoxidation Rice pollard oil, epoxidation sunflower oil.The more kind of foreign study, except the epoxidation soybean oil, mainly also concentrated on the research of epoxidized vegetable oil class, epoxy aliphatic ester class (biofuel) in recent years.
Epoxidized vegetable oil class softening agent is started late in China, and development is slow, mainly take epoxy soybean oil as main.Other kind such as epoxy oleum lini, epoxy cottonseed oil etc. are not well developed, and small scale, dispersion do not form scale output, the automatic control level is low.The throughput of most of factories is at 300t/a～500t/a, and the most of sulfuric acid catalysis production technique of making solvent with benzene, batch production of adopting.Unstable product quality, price is higher, unfavorable expansion market.Thereby Devoting Major Efforts To Developing research epoxidized vegetable oil new variety are answered in softening agent industry, improve level of control, form serialization production, realize economic scale output, reduce costs, to adapt to the needs of plastics industry development.
Softening agent mainly be take adjacent benzene-type products as main for a long time, but along with the application of DOP on food, medicine industry is more and more extensive, people also more and more pay attention to its toxicity.U.S. environment protection general bureau is according to the result of study of National Cancer Institute, stopped the production of 6 kinds of new phthalate industry, DOP is only limited in the food product pack of high water content and uses, and meat Package must substitute with other non-toxic plasticizer product; Switzerland government has determined to ban use of DOP in toy for children; Germany forbids adding DOP in all plastics relevant to human physiology, food; Japan forbids adding DOP in the medicine equipment related products, only limit to apply in the industrial plastic goods.At present, the research and development of non-toxic plasticizer product have been accelerated in the whole world, have accelerated especially the high plastics base application research of hygienic requirements.Development obviously lags behind the needs of producing and living for environment-friendly plasticizer in the world at present, along with scientific and technological progress, some traditional materials may be eliminated, and the novel environment friendly softening agent of researching and developing the advantage such as harmless, inexpensive, that auxiliary agent is effective material as an alternative is key one ring of plasthetics industry development instantly.
At present, the softening agent that China is used, principal item is phthalic ester (butyl ester, monooctyl ester) and epoxy soybean oil, Oleum Gossypii semen is at the aboundresources of China, it obtains epoxy through esterification, epoxidation and does the softening agent use, be subject in recent years extensive attention, the more above-mentioned two kinds of softening agent of its cost are low after deliberation, the more above-mentioned two kinds of softening agent of some index of its performance are superior, and epoxy aliphatic acid methyl ester is compared with epoxy soybean oil, can greatly improve the adding proportion that adds man-hour at the PVC goods, adding proportion can be up to 30%, therefore very big development prospect is arranged.The Oleum Gossypii semen epoxy plasticizer is cold-resistant, fast light heat, and good stability, nontoxic, can be used for the exterior and interior packing of food and medicine, agricultural film, leatheroid, plastic floor, electric heating sheath, light technique film industrial circle.
Summary of the invention
The environment-friendly type plasticizer production process that the purpose of this invention is to provide a kind of high epoxy value, this raw materials technology is easy to get, technique advanced, equipment is simple, when making the environment-friendly type softening agent of high epoxy value, its byproduct Uniphat A60 can be used as the high quality raw material of production environment-friendly type tensio-active agent (MES).
Technical scheme of the present invention is: a kind of high epoxy value environment-friendly type plasticizer production process, it is characterized in that,
(1) Oleum Gossypii semen, methyl alcohol (content 99.5wt%) and sodium methylate are sent into to transesterification reactor and carried out transesterification reaction and obtain mixed methyl aliphatic ester and glycerine, temperature of reaction is 70-90 ℃, and the reaction times is 30 minutes; The weight percentage of described Oleum Gossypii semen, methyl alcohol (content 99.5wt%) and sodium methylate is respectively Oleum Gossypii semen 78.5-84.5%, methyl alcohol (content 99.5%) 15.2-21.2%, and sodium methylate 0.3-0.4%, its total amount is 100%;
This reacts esterification yield >=99%, fatty acid methyl ester iodine number≤0.1, acid number≤0.5, moisture content≤0.1%, free oil≤2%.
(2) staticly settle and isolate glycerine, then mixed methyl aliphatic ester is sent into to the material filling type rectifying tower and carried out rectifying separation, column bottom temperature 225-245 ℃, tower top temperature 175-195 ℃, vacuum tightness 0.09Mpa, reflux ratio is 2-6; After rectifying, obtain respectively Witconol 2301 and Uniphat A60 from the bottom of tower and tower top;
(3) from out Witconol 2301 at the bottom of tower, enter in the epoxidation reaction still, add the acidic ion exchange resin of Witconol 2301 quality 7-12% to do the aqueous solution that contains the 27-50wt% hydrogen peroxide of catalyzer and Witconol 2301 quality 25-40%, the concentration that drips Witconol 2301 quality 10-15% under stirring state is that the industrial formic acid of 80-90wt% reacts, in 15-30 minute, dropwise, dropwise rear continuation reaction 20-30 minute; In dropping and reaction process, controlling temperature of reaction is 55-85 ℃; The above hydrogen peroxide is produced by hydroxyl radical free radical oxygengenerator scene.
(4) stratification after reaction terminating, minute sub-cloud mother liquor; Product neutralizes with weak lye, more extremely neutral with the soft water washing; Then be evacuated in dehydrating kettle, vacuum removal wherein namely obtains high epoxy value environment-friendly type softening agent after institute's water content; Product oxirane value >=7.0, yield are 80-85%.
The preparation of environment-friendly type tensio-active agent of the present invention (MES) by product:
(1) Uniphat A60 and the sulphur trioxide that the material filling type rectifier are obtained carry out sulfonation reaction, generate methyl esters sulfonic acid, temperature of reaction is 80-85 ℃, and the reaction times is 10-20 minute, and the mol ratio of described Uniphat A60 and sulphur trioxide is 1: 1.06～1: 1.25;
(2) then heat up, aging 25-35 minute under temperature 90-95 ℃, the acid product after aging adds the methyl alcohol of its (acid product after aging) quality 3-8% to carry out esterification, reaction times 20-30 minute; In esterification reaction process, add the aqueous solution that contains the 27wt% hydrogen peroxide to carry out continuous bleaching, bleaching temperature is controlled at 65-75 ℃, and the total amount that adds that contains the aqueous solution of 27wt% hydrogen peroxide is the 5-10% of the acid product quality after aging;
(3) then product is squeezed into to neutralization reactor, adding mass percentage concentration is that 30% liquid caustic soda neutralizes continuously, and temperature is controlled at 45 ± 5 ℃; Neutralized reaction product enters flashing tower and reclaims methyl alcohol, advances the turbulent flow moisture eliminator and carries out namely obtaining environment-friendly type tensio-active agent MES (active matter content >=80%) after drying.
The invention has the beneficial effects as follows: raw materials technology is easy to get, and the technique sophisticated equipment is simple, can make the softening agent of high epoxy value (oxirane value >=7.0), but and its byproduct Uniphat A60 production environment-friendly type tensio-active agent.
Embodiment
Embodiment 1
The present invention prepares the method for high epoxy value environment-friendly type softening agent,
(1) 78.6% refined cottonseed oil and 21% methyl alcohol (content 99.5%) and 0.4% sodium methylate are entered continuously in transesterification reactor and carry out transesterification reaction, it is 30 minutes that temperature of reaction is controlled at 85 ℃, reaction times, obtains mixed methyl aliphatic ester and glycerine.Staticly settle and isolate glycerine.Esterification yield is 99.2%, fatty acid methyl ester iodine number≤0.1, acid number≤0.5, moisture content≤0.1%, free oil≤2%.
(2) mixed methyl aliphatic ester enters the material filling type rectifying tower and carries out rectifying separation, controls 190 ℃ of tower top temperatures, 240 ℃ of column bottom temperatures, and vacuum tightness 0.09Mpa, reflux ratio is 2.
(3) from rectifier bottoms Witconol 2301 out, enter in the epoxidation reaction still, add 001 * 7 type acidic ion exchange resin of Witconol 2301 quality 10% to do the aqueous solution that contains the 28wt% hydrogen peroxide of catalyzer and Witconol 2301 quality 25%, the concentration that drips Witconol 2301 quality 10% under stirring state is that the industrial formic acid of 85wt% reacts, in 15 minutes, dropwise, dropwise rear continuation reaction 25 minutes; Dropping and reaction process are controlled temperature of reaction at 75-80 ℃ with chilled brine.Stratification after reaction terminating, minute sub-cloud mother liquor; Product neutralizes with weak lye, more extremely neutral with the soft water washing; Then be evacuated in dehydrating kettle, vacuum removal wherein namely obtains high epoxy value environment-friendly type softening agent after institute's water content; Oxirane value is 7.5, and yield is 80.5%;
The preparation of by product environmental protection tensio-active agent (MES):
(1) from rectifier, get Uniphat A60, with sulphur trioxide, carried out sulfonation reaction 15 minutes 80 ℃ of temperature, generate methyl esters sulfonic acid; The mol ratio of described Uniphat A60 and sulphur trioxide is 1: 1.1.
(2) then heat up, at 90 ℃ of temperature aging 25 minutes, the acid product after aging added the methyl alcohol of its quality 6% to carry out esterification, 20 minutes reaction times; In esterification reaction process, add the aqueous solution that contains the 27wt% hydrogen peroxide to carry out continuous bleaching, bleaching temperature is controlled at 70 ℃, contain the 27wt% hydrogen peroxide the aqueous solution add total amount be after aging the acid product quality 5%.
(3) then product is squeezed into to neutralization reactor and added the liquid caustic soda of concentration 30% to neutralize continuously, temperature is controlled at 43-48 ℃.Neutralized reaction product enters flashing tower and reclaims methyl alcohol, advances the turbulent flow moisture eliminator and carries out namely obtaining environment-friendly type tensio-active agent MES (active matter content 80%) after drying.
Embodiment 2
The present invention prepares the method for high epoxy value environment-friendly type softening agent
(1) 80% refined cottonseed oil and 19.7% methyl alcohol (content 99.5%) and 0.3% sodium methylate are entered continuously in transesterification reactor and carry out transesterification reaction, it is 30 minutes that temperature of reaction is controlled at 80 ℃, reaction times, obtain mixed methyl aliphatic ester and glycerine, staticly settle and isolate glycerine.Esterification yield is 99.5%, fatty acid methyl ester iodine number≤0.1, acid number≤0.5, moisture content≤0.1%, free oil≤2%.
(2) mixed methyl aliphatic ester enters the material filling type rectifying tower and carries out rectifying separation, controls 195 ℃ of tower top temperatures, 245 ℃ of column bottom temperatures, and vacuum tightness 0.09Mpa, reflux ratio is 4.
(3) from rectifier bottoms Witconol 2301 out, enter in the epoxidation reaction still, add 001 * 7 type acidic ion exchange resin of Witconol 2301 quality 12% to do the aqueous solution that contains the 27wt% hydrogen peroxide of catalyzer and Witconol 2301 quality 30%, the concentration that drips Witconol 2301 quality 12% under stirring state is that the industrial formic acid of 85wt% reacts, in 20 minutes, dropwise, dropwise rear continuation reaction 30 minutes; Dropping and reaction process are controlled temperature of reaction at 75-80 ℃ with chilled brine.Stratification after reaction terminating, minute sub-cloud mother liquor; Product neutralizes with weak lye, more extremely neutral with the soft water washing; Then be evacuated in dehydrating kettle, in vacuum removal oil, namely obtain high epoxy value environment-friendly type softening agent after institute's water content; Its oxirane value is 7.0, and yield is 85%.
The preparation of by product environmental protection tensio-active agent (MES):
(1) from rectifier, get Uniphat A60, with sulphur trioxide, carried out sulfonation reaction 15 minutes 85 ℃ of temperature, generate methyl esters sulfonic acid; The mol ratio of described Uniphat A60 and sulphur trioxide is 1: 1.25.
(2) then heat up, at 95 ℃ of temperature aging 30 minutes, the acid product after aging added the methyl alcohol of its quality 5% to carry out esterification, 25 minutes reaction times; In esterification reaction process, add the aqueous solution that contains the 27wt% hydrogen peroxide to carry out continuous bleaching, bleaching temperature is controlled at 70 ℃, contain the 27wt% hydrogen peroxide the aqueous solution add total amount be after aging the acid product quality 8%.
(3) then product is squeezed into to neutralization reactor and added the liquid caustic soda of concentration 30% to neutralize continuously, temperature is controlled at 43-48 ℃.Neutralized reaction product enters flashing tower and reclaims methyl alcohol, advances the turbulent flow moisture eliminator and carries out namely obtaining environment-friendly type tensio-active agent MES (active matter content 81%) after drying.
Embodiment 3
The present invention prepares the method for high epoxy value environment-friendly type softening agent
(1) 84.5% refined cottonseed oil and 15.2% methyl alcohol (content 99.5%) and 0.3% sodium methylate are entered continuously in transesterification reactor and carry out transesterification reaction, it is 30 minutes that temperature of reaction is controlled at 90 ℃, reaction times, obtains mixed methyl aliphatic ester and glycerine.Staticly settle and isolate glycerine.Esterification yield is 99.3%, fatty acid methyl ester iodine number≤0.1, acid number≤0.5, moisture content≤0.1%, free oil≤2%.
(2) mixed methyl aliphatic ester enters the material filling type rectifying tower and carries out rectifying separation, controls 175 ℃ of tower top temperatures, 225 ℃ of column bottom temperatures, and vacuum tightness 0.09Mpa, reflux ratio is 5.
(3) from rectifier bottoms Witconol 2301 out, enter in the epoxidation reaction still, add 001 * 7 type acidic ion exchange resin of Witconol 2301 quality 7% to do the aqueous solution that contains the 27wt% hydrogen peroxide of catalyzer and Witconol 2301 quality 25%, the concentration that drips Witconol 2301 quality 15% under stirring state is that the industrial formic acid of 85wt% reacts, in 30 minutes, dropwise, dropwise rear continuation reaction 20 minutes; Dropping and reaction process are controlled temperature of reaction at 75-80 ℃ with chilled brine.Stratification after reaction terminating, minute sub-cloud mother liquor; Product neutralizes with weak lye, more extremely neutral with the soft water washing; Then be evacuated in dehydrating kettle, in vacuum removal oil, namely obtain high epoxy value environment-friendly type softening agent after institute's water content; Oxirane value is 7.2, and yield is 82.0%;
The preparation of by product environmental protection tensio-active agent (MES):
(1) from rectifier, get Uniphat A60, with sulphur trioxide, carried out sulfonation reaction 20 minutes 80 ℃ of temperature, generate methyl esters sulfonic acid; The mol ratio of described Uniphat A60 and sulphur trioxide is 1: 1.06.
(2) then heat up, at 95 ℃ of temperature aging 30 minutes, the acid product after aging added the methyl alcohol of its quality 8% to carry out esterification, 20 minutes reaction times; In esterification reaction process, add the aqueous solution that contains the 27wt% hydrogen peroxide to carry out continuous bleaching, bleaching temperature is controlled at 65 ℃, contain the 27wt% hydrogen peroxide the aqueous solution add total amount be after aging the acid product quality 10%.
(3) then product is squeezed into to neutralization reactor and added the liquid caustic soda of concentration 30% to neutralize continuously, temperature is controlled at 40-45 ℃.Neutralized reaction product enters flashing tower and reclaims methyl alcohol, advances the turbulent flow moisture eliminator and carries out namely obtaining environment-friendly type tensio-active agent MES (active matter content 81.5%) after drying.
Claims (2)
1. a high epoxy value environment-friendly type plasticizer production process, is characterized in that, comprises the following steps:
(1) Oleum Gossypii semen, methyl alcohol and sodium methylate are sent into to transesterification reactor and carried out transesterification reaction and obtain mixed methyl aliphatic ester and glycerine, temperature of reaction is 70-90 ℃, and the reaction times is 30 minutes; The weight percentage of described Oleum Gossypii semen, methyl alcohol and sodium methylate is respectively Oleum Gossypii semen 78.5-84.5%, methyl alcohol 15.2-21.2%, and sodium methylate 0.3-0.4%, its total amount is 100%; Described methanol content is 99.5%;
(2) staticly settle and isolate glycerine, then mixed methyl aliphatic ester is sent into to the material filling type rectifying tower and carried out rectifying separation, column bottom temperature 225-245 ℃, tower top temperature 175-195 ℃, vacuum tightness 0.09Mpa, reflux ratio is 2-6; After rectifying, obtain respectively Witconol 2301 and Uniphat A60 from the bottom of tower and tower top;
(3) from out Witconol 2301 at the bottom of tower, enter in the epoxidation reaction still, add the acidic ion exchange resin of Witconol 2301 quality 7-12% to do the aqueous solution that contains the 27-50wt% hydrogen peroxide of catalyzer and Witconol 2301 quality 25-40%, the concentration that drips Witconol 2301 quality 10-15% under stirring state is that the industrial formic acid of 80-90wt% reacts, in 15-30 minute, dropwise, dropwise rear continuation reaction 20-30 minute; In dropping and reaction process, controlling temperature of reaction is 55-85 ℃;
(4) stratification after reaction terminating, minute sub-cloud mother liquor; Product neutralizes with weak lye, more extremely neutral with the soft water washing; Then be evacuated in dehydrating kettle, vacuum removal wherein namely obtains high epoxy value environment-friendly type softening agent after institute's water content.
2. an environment-friendly type tensio-active agent MES production technique, is characterized in that, comprises the following steps:
(1) Uniphat A60 and the sulphur trioxide that the material filling type rectifier are obtained carry out sulfonation reaction, generate methyl esters sulfonic acid, temperature of reaction is 80-85 ℃, and the reaction times is 10-20 minute, and the mol ratio of described Uniphat A60 and sulphur trioxide is 1:1.06～1:1.25;
(2) then heat up, aging 25-35 minute under temperature 90-95 ℃, the acid product after aging adds the methyl alcohol of its quality 3-8% to carry out esterification, reaction times 20-30 minute; In esterification reaction process, add the aqueous solution that contains the 27wt% hydrogen peroxide to carry out continuous bleaching, bleaching temperature is controlled at 65-75 ℃, and the total amount that adds that contains the aqueous solution of 27wt% hydrogen peroxide is the 5-10% of the acid product quality after aging;
(3) then product is squeezed into to neutralization reactor, adding mass percentage concentration is that 30% liquid caustic soda neutralizes continuously, and temperature is controlled at 45 ± 5 ℃; Neutralized reaction product enters flashing tower and reclaims methyl alcohol, advances the turbulent flow moisture eliminator and carries out namely obtaining environment-friendly type tensio-active agent MES after drying.
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| CN103111329B (en) * | 2013-01-21 | 2015-01-07 | 江南大学 | Preparation method and application of heterogeneous epoxy catalyst |
| CN103224459A (en) * | 2013-04-13 | 2013-07-31 | 齐河县齐翔生物科技有限公司 | Method for producing fatty acid methyl ester sulfonate by using waste oil |
| CN106519081B (en) * | 2016-09-22 | 2018-06-26 | 深圳立山环保材料有限公司 | A kind of epoxy plasticiser and preparation method thereof |
| CN107354010A (en) * | 2017-08-02 | 2017-11-17 | 合肥万之景门窗有限公司 | A kind of preparation method of plasticizer for plastic-steel door and window |
| CN108410584A (en) * | 2018-04-01 | 2018-08-17 | 汕头市龙琪塑料制品有限公司 | A kind of preparation method of medicine bottle natural rice bran fatty acid oil plasticizer |
| CN114854148B (en) * | 2022-05-27 | 2023-11-10 | 中国第一汽车股份有限公司 | Polyvinyl chloride composite material and preparation method and application thereof |
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| JPH0798957B2 (en) * | 1988-09-29 | 1995-10-25 | 不二製油株式会社 | Method for producing fats and oils for emulsified foods |
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