CN102978010B - Process method for producing epoxidized soybean oil by using crude soybean oil as raw material - Google Patents
Process method for producing epoxidized soybean oil by using crude soybean oil as raw material Download PDFInfo
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- CN102978010B CN102978010B CN201210512531.XA CN201210512531A CN102978010B CN 102978010 B CN102978010 B CN 102978010B CN 201210512531 A CN201210512531 A CN 201210512531A CN 102978010 B CN102978010 B CN 102978010B
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- soybean oil
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- 239000003549 soybean oil Substances 0.000 title claims abstract description 28
- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000003921 oil Substances 0.000 claims abstract description 25
- 235000019198 oils Nutrition 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 235000010469 Glycine max Nutrition 0.000 claims description 32
- 244000068988 Glycine max Species 0.000 claims description 32
- 239000010779 crude oil Substances 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 150000003904 phospholipids Chemical class 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 210000002683 foot Anatomy 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000003513 alkali Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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Abstract
The invention provides a method for producing epoxidized soybean oil by using crude soybean oil as a raw material. The method is characterized by comprising the following steps of: 1, mixing four grades of crude soybean oil with phosphoric acid, settling until separation of oil foots, removing the remaining phospholipid from an oil layer through membrane treatment, then raising the temperature to be between 50 and 90 DEG C, keeping the temperature constant for 10 to 30 minutes, cooling and mixing with thin lye, and after mixing, keeping the temperature of the system constant at 100 DEG C for 45 minutes and then performing centrifugal separation to obtain treated crude soybean oil; and 2, under a microwave condition, dripping urea peroxide into the oil obtained in the step 1 for epoxidation, neutralizing the mixture with thin lye, performing water-washing, separating the oil from the water, and dehydrating to obtain finished epoxidized soybean oil. The epoxide number of the finished epoxidized soybean oil obtained by the method can be between 6.0 and 6.5 and the acid number is reduced to be below 0.6 mgKOH/g.
Description
Technical field
The present invention relates to a kind of method take crude oil of soybean as raw material production epoxy soybean oil.
Background technology
Epoxy soybean oil is domestic and international Application and Development a kind of epoxy plasticizer early, there is good thermostability, light stability, water tolerance and oil-proofness, developed into the third-largest class softening agent, be widely used in the goods such as nontoxic PVC film, drug packages, plastic door-window, tubing, house decorative material, electric wire, medical apparatus, toy for children, cultural goods.
Prior art is all using the purified soyabean oil of environmental protection as the main raw of producing epoxy soybean oil, thereby production cost is very high.For reducing production costs, increase the competitive capacity in market, find raw materials for production cheaply and substitute purified soyabean oil, become the research and development merit pass problem of each production epoxy soybean oil producer.
Summary of the invention
The object of the invention is to provide a kind of method of producing epoxy soybean oil with crude oil of soybean, cost is low, and technique is simple, and operational safety can meet commercial scale production.
In order to achieve the above object, the invention provides a kind of method take crude oil of soybean as raw material production epoxy soybean oil, it is characterized in that, concrete steps are:
The first step: the phosphoric acid that is 85% with concentration by level Four crude oil of soybean mixes 1～10min, phosphoric acid consumption is the 0.2%-2% of crude oil of soybean weight, mixing temperature is 20～50 ℃, sedimentation removes sub-cloud soap stock for 2 hours, supernatant liquid is warming up to 50～90 ℃ after removing residue phosphatide by film processing, insulation 10～30min, then be cooled to 20～50 ℃, the rare potassium hydroxide aqueous solution that is 5～20Be ' with concentration again mixes drops to below 1 acid value, be heated to 100 ℃, insulation 45min, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
Second step: under microwave condition, in the crude oil of soybean obtaining to the first step, drip concentration and be 10% urea peroxide solution and carry out epoxy reaction, the add-on of urea peroxide solution be oil heavy 40%, temperature is controlled at 50-100 ℃, reaction 4-10 hour;
The 3rd step: the dilute alkaline soln that is 1-10Be ' by concentration by the reaction product of second step gained neutralization, washing, oily water separation, then decompression dehydration obtains finished product epoxy soybean oil.
The oxirane value of the finished product epoxy soybean oil that the present invention obtains can reach 6.0-6.5, and acid number drops to below 0.6mgKOH/g.
Compared with prior art, advantage of the present invention is:
1, the present invention is take level Four crude oil of soybean as raw material, and film is processed oil can make wherein phospholipids content be down to below 10ppm, is more conducive to the carrying out of epoxidation reaction.
2, urea peroxide has stronger reactive behavior, can impel the carrying out of epoxidation reaction.The oxirane value of finished product epoxy soybean oil of the present invention can reach 6.0-6.5, and acid number drops to below 0.6mgKOH/g.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.In each embodiment, the testing method that acid number adopts adopts the mensuration of GB/T1668-2008 softening agent acid number and acidity, and the testing method of oxirane value adopts the mensuration of GB/T 1677-2008 softening agent oxirane value.
Embodiment 1
A method take crude oil of soybean as raw material production epoxy soybean oil, specific as follows:
(1) to raw material level Four crude oil of soybean, (iodine number is 128%, acid number 1.3mgKOH/g) in add oil to weigh the phosphoric acid solution that 0.3% concentration is 85%, after temperature remains on and mixes 10min at 50 ℃, sedimentation 2h is except sub-cloud oil foot, supernatant liquid is processed after residue phosphatide is removed and is warming up to 80 ℃ by film, and constant temperature 30min, then be cooled to 50 ℃, and mix and make acid value reduce to 0.8 with rare potassium hydroxide aqueous solution, concentration of lye is 15Be ', alkali lye consumption calculates according to acid value, and calculation formula is: actual alkali charge=oil weight × acid value × 1.3 × 10
-3/ alkali lye massfraction, rises to 100 ℃ of insulation 45min by mixeding liquid temperature, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
(2) under microwave condition (power is 648W), in the crude oil of soybean obtaining to the first step, dripping in batches concentration is the 10% urea peroxide aqueous solution, the add-on of urea peroxide solution is that oil is heavy by 40%, and this epoxy reaction temperature is controlled at 80 ℃, 10 hours time;
(3) sodium hydroxide solution that is 10Be ' by the reaction product of gained by concentration neutralization, till being neutrality to water layer, washing, dehydration obtains finished product epoxy soybean oil, products obtained therefrom oxirane value 6.1%, acid number 0.6mgKOH/g, color and luster 160# (platinum cobalt colorimetry).
Embodiment 2
A method take crude oil of soybean as raw material production epoxy soybean oil, specific as follows:
(1) to raw material level Four crude oil of soybean, (iodine number is 128%, acid number 1.3mgKOH/g) in add oil to weigh the phosphoric acid solution that 0.3% concentration is 85%, after temperature remains on and mixes 10min at 50 ℃, sedimentation 2h is except sub-cloud oil foot, supernatant liquid is processed after residue phosphatide is removed and is warming up to 90 ℃ by film, and constant temperature 30min, then be cooled to 50 ℃, and mix and make acid value reduce to 0.8 with rare potassium hydroxide aqueous solution, concentration of lye is 20Be ', alkali lye consumption calculates according to acid value, and calculation formula is: actual alkali charge=oil weight × acid value × 1.3 × 10
-3/ alkali lye massfraction, rises to 100 ℃ of insulation 45min by mixeding liquid temperature, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
(2) under microwave condition (power is 648W), in the crude oil of soybean obtaining to the first step, drip in batches concentration and be 10% the urea peroxide aqueous solution, the add-on of urea peroxide solution is that oil is heavy by 40%, and this epoxy reaction temperature is controlled at 90 ℃, 10 hours time;
(3) sodium hydroxide solution that is 10Be ' by the reaction product of gained by concentration neutralization, till being neutrality to water layer, washing, dehydration obtains finished product epoxy soybean oil, products obtained therefrom oxirane value 6.5%, acid number 0.6mgKOH/g, color and luster 130# (platinum cobalt colorimetry).
Embodiment 3
A method take crude oil of soybean as raw material production epoxy soybean oil, specific as follows:
(1) to raw material level Four crude oil of soybean, (iodine number is 128%, acid number 1.3mgKOH/g) in add oil to weigh the phosphoric acid solution that 0.3% concentration is 85%, after temperature remains on and mixes 10min at 30 ℃, sedimentation 2h is except sub-cloud oil foot, supernatant liquid is processed after residue phosphatide is removed and is warming up to 70 ℃ by film, and constant temperature 30min, then be cooled to 20 ℃, and mix and make acid value reduce to 0.7 with rare potassium hydroxide aqueous solution, concentration of lye is 10Be ', alkali lye consumption calculates according to acid value, and calculation formula is: actual alkali charge=oil weight × acid value × 1.3 × 10
-3/ alkali lye massfraction, rises to 100 ℃ of insulation 45min by mixeding liquid temperature, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
(2) under microwave condition (power is 648W), in the crude oil of soybean obtaining to the first step, drip in batches concentration and be 10% the urea peroxide aqueous solution, the add-on of urea peroxide solution is that oil is heavy by 40%, and this epoxy reaction temperature is controlled at 100 ℃, 6 hours time;
(3) sodium hydroxide solution that is 10Be ' by the reaction product of gained by concentration neutralization, till being neutrality to water layer, washing, dehydration obtains finished product epoxy soybean oil, products obtained therefrom oxirane value 6.1%, acid number 0.6mgKOH/g, color and luster 130# (platinum cobalt colorimetry).
Embodiment 4
A method take crude oil of soybean as raw material production epoxy soybean oil, specific as follows:
(1) to raw material level Four crude oil of soybean, (iodine number is 128%, acid number 1.3mgKOH/g) in add oil to weigh the phosphoric acid solution that 0.3% concentration is 85%, after temperature remains on and mixes 10min at 50 ℃, sedimentation 2h is except sub-cloud oil foot, supernatant liquid is processed after residue phosphatide is removed and is warming up to 90 ℃ by film, and constant temperature 10min, then be cooled to 50 ℃, and mix and make acid value reduce to 0.7 with rare potassium hydroxide aqueous solution, concentration of lye is 5Be ', alkali lye consumption calculates according to acid value, and calculation formula is: actual alkali charge=oil weight × acid value × 1.3 × 10
-3/ alkali lye massfraction, rises to 100 ℃ of insulation 45min by mixeding liquid temperature, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
(2) under microwave condition (power is 648W), in the crude oil of soybean obtaining to the first step, drip in batches concentration and be 10% the urea peroxide aqueous solution, the add-on of urea peroxide solution is that oil is heavy by 40%, and this epoxy reaction temperature is controlled at 100 ℃, 10 hours time
(3) sodium hydroxide solution that is 5Be ' by the reaction product of gained by concentration neutralization, till being neutrality to water layer, washing, dehydration obtains finished product epoxy soybean oil, products obtained therefrom oxirane value 6.3%, acid number 0.6mgKOH/g, color and luster 160# (platinum cobalt colorimetry).
Claims (1)
1. the method take crude oil of soybean as raw material production epoxy soybean oil, is characterized in that, concrete steps are:
The first step: the phosphoric acid that is 85% with concentration by level Four crude oil of soybean mixes 1～10min, phosphoric acid consumption is the 0.2%-2% of crude oil of soybean weight, mixing temperature is 20～50 ℃, sedimentation removes sub-cloud soap stock for 2 hours, supernatant liquid is warming up to 50～90 ℃ after removing residue phosphatide by film processing, insulation 10～30min, then be cooled to 20～50 ℃, the rare potassium hydroxide aqueous solution that is 5～20Be ' with concentration again mixes drops to below 1 acid value, be heated to 100 ℃, insulation 45min, finally enters butterfly centrifugal machine and separates, the crude oil of soybean that obtains processing;
Second step: under microwave condition, in the crude oil of soybean obtaining to the first step, drip concentration and be 10% urea peroxide solution and carry out epoxy reaction, the add-on of urea peroxide solution be oil heavy 40%, temperature is controlled at 50-100 ℃, reaction 4-10 hour;
The 3rd step: the dilute alkaline soln that is 1-10Be ' by concentration by the reaction product of second step gained neutralization, washing, oily water separation, then decompression dehydration obtains finished product epoxy soybean oil.
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| CN104262297B (en) * | 2014-09-01 | 2016-03-16 | 南京工业大学 | Method for preparing high-quality epoxy vegetable oil by adopting microreactor |
| CN105254596A (en) * | 2015-09-18 | 2016-01-20 | 丹阳市助剂化工厂有限公司 | Preparation method for epoxidized soybean oil |
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| JP4007656B2 (en) * | 1997-11-27 | 2007-11-14 | 株式会社Ａｄｅｋａ | Epoxidized animal and vegetable oil composition |
| CN101338042B (en) * | 2008-08-11 | 2011-01-26 | 浙江嘉澳环保科技股份有限公司 | Method for preparing biodegradable composite plasticiser |
| CN101591588A (en) * | 2009-06-24 | 2009-12-02 | 江南大学 | Organic rhenium oxide-carbamide peroxide catalyzes the method for preparing epoxy soybean oil or epoxy fatty acid methyl (ethyl) ester |
| CN102250693B (en) * | 2011-06-21 | 2013-12-11 | 广州市新锦龙实业有限公司 | Process flow for preparing epoxidized soybean oil by using crude soybean oil |
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