CN102161938B - Method for producing epoxy fatty acid methyl ester by using illegal cooking oil - Google Patents
Method for producing epoxy fatty acid methyl ester by using illegal cooking oil Download PDFInfo
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Abstract
The invention relates to a method for producing epoxy fatty acid methyl ester by using illegal cooking oil, which comprises: subjecting illegal cooking oil and methanol to esterification to obtain fatty acid methyl ester; purifying the fatty acid methyl ester by molecular distillation and performing epoxidation; and subjecting the obtained crude fatty acid methyl ester to three-stage rectification to obtain three models of epoxy fatty acid methyl ester. In the invention, illegal cooking oil is used as a raw material, and esterification is performed under normal pressure; as the reaction temperature is higher than the boiling point of methanol, the methanol is gasified immediately upon contact with fat; and the methanol is uniformly, quickly and fully contacted with the fat, so the esterification speed is further improved. When the method is used, the illegal cooking oil waste is utilized, cost is saved, environment is protected, energy consumption is low, process is simple, operation is safe and product quality is high. Therefore, the method is a resource-saving and environment-friendly production method. The epoxide number of the obtained No.1 epoxy fatty acid methyl ester is 4.0 to 5.0, the plasticizing effect of the epoxy fatty acid methyl ester is desirable, the acid value is smaller than 1, the saponification of plasticized products is avoided, a flashing point is above 180 DEG C, an iodine value is smaller than 3, and the epoxy fatty acid methyl ester passed the verification of quality supervision and inspection departments and are approved to be qualified.
Description
Technical field
The present invention relates to a kind of method of producing epoxy aliphatic acid methyl ester with sewer oil.
Background technology
Enhancing along with human environmental consciousness, the toxicity of softening agent more and more receives people's concern, traditional phthalic ester plasticizer (DOP, DBP) is because there are carcinogenic possibility many fields abroad disabled, and the emerging softening agent such as citric acid ester type, epoxy compounds class are favored because of environmental protection.Present epoxy plasticizer is take epoxy soybean oil as main, and the epoxy soybean oil mode of production is single, cost is high, profit is low, do not have good economic and social benefit, and development space is little.Epoxy aliphatic acid methyl ester is a kind of new plasticizer, because its environment-protecting asepsis, anti-aging, transparent, light and good heat stability have wide market outlook.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technique is simple, energy consumption is low, environmental protection and can obtain the method for producing epoxy aliphatic acid methyl ester with sewer oil of three kinds of different standards products.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of method of producing epoxy aliphatic acid methyl ester with sewer oil is characterized in that it comprises the steps:
(1) by weight percentage the sewer oil of 95-99.8% and the sulfuric acid of 0.2-5% are added in the reactor, be heated to 75-85 ℃, drip methyl alcohol and carry out esterification, methyl alcohol rate of addition 150-200kg/h, methanol usage is sewer oil 120-160kg per ton, reaction times 8-10h after reaction finishes, tells the glycerine of lower floor, add in the sodium hydroxide of its weight 5-8% in the supernatant liquid and unnecessary sulfuric acid, standing demix again, the upper strata is crude fatty acid methyl ester, is isolated out stand-by;
(2) crude fatty acid methyl ester that obtains in the step (1) is carried out the molecule rectification and purification under 200-220 ℃, vacuum tightness 0.1-10Pa, isolate colloid and plant asphalt, the fatty acid methyl ester that obtains purifying;
(3) fatty acid methyl ester that step (2) is obtained is squeezed into reactor, add the hydrogen peroxide of its weight 30-35%, the formic acid of 6-10% and the sulfuric acid of 5-10%, under 75-85 ℃, 3-7Pa, stir and carried out epoxidation reaction in 12-14 hour, after epoxidation reaction finishes, standing demix is told the sour water of lower floor, adds the alkali rear recycling that neutralizes, upper solution is put into dehydration tower, obtains thick epoxy aliphatic acid methyl ester after sloughing moisture content;
(4) the thick epoxy aliphatic acid methyl ester that obtains in the step (3) is carried out the epoxy aliphatic acid methyl ester that three grades of rectifying obtain three kinds of models.
The condition of described three grades of rectifying is respectively:
One-level rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 1:1;
Two-stage rectification: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 3:1;
Three grades of rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 6:1.
Positively effect of the present invention is: the present invention is take sewer oil as raw material, under normal pressure, carry out esterification, temperature is between 75-85 ℃, be pyroreaction, temperature of reaction is higher than 67 ℃ of the boiling points of methyl alcohol, so methyl alcohol and at once gasification after grease contacts can make methyl alcohol evenly, fully contact with grease rapidly, further the speed of enhance esterification.The present invention adopts the recycled for multiple times of methyl alcohol, has not only reduced methanol usage, and energy consumption is low, and can conveniently control and regulate methanol usage, is convenient to produce.The present invention adopts the molecule distillation technology, and reacted by product is few, and grease can repeatedly use, and the fatty acid methyl ester smell after the purification is little, and acid number is low, for epoxy reaction is laid good basis.The oxirane value of the 1# epoxy aliphatic acid methyl ester that the inventive method obtains is 4.0-5.0, and plasticization effect is good, and acid number is less than 1, can not make and mould product saponification processed, flash-point is more than 180 ℃, and it is qualified that iodine number is assert less than 12 Nikkei Hebei province product quality supervision inspection institutes check in 3,2010 year April.
But the acid recycled for multiple times that produces in the inventive method, glycerine is used for GC stationary liquid and organic synthesis, also can be used as solvent, tolerance and take into account water pressure engine shock absorber fluid, tenderizer, antibiotic fermentation with nutrition agent, siccative etc., and with the sewer oil utilization of waste material, not only saved cost, and environmental protection, energy consumption is low, and technique is simple, operational safety, quality product is high, is resource-conserving, environmentally friendly production method.
Embodiment
Following examples are to further specify of the present invention, rather than limit its scope.
Embodiment 1
(1) by weight percentage the sulfuric acid of 95% sewer oil and 5% is added in the reactor, be heated to 75-85 ℃, drip methyl alcohol and carry out esterification, methyl alcohol rate of addition 180kg/h, methanol usage is sewer oil 120kg per ton, reaction times 8h, simultaneously recovery steams condensed methyl alcohol and puts into the use of methanol rectifying tower Recovery and recycle, after reaction finishes, tell the glycerine of lower floor, add in the sodium hydroxide of its weight 5% in the supernatant liquid and unnecessary sulfuric acid, standing demix again, the upper strata is crude fatty acid methyl ester;
(2) crude fatty acid methyl ester that obtains in the step (1) is carried out the molecule rectification and purification, distillation temperature is 200-220 ℃, and vacuum tightness is 0.1-10Pa, isolates colloid and plant asphalt, the fatty acid methyl ester that obtains purifying;
(3) fatty acid methyl ester after step (2) purification is squeezed into reactor, the hydrogen peroxide, 8% formic acid and 5% the sulfuric acid that add its weight 35%, under 75-85 ℃, 7-10Pa pressure-fired, stir and carried out epoxidation reaction in 12 hours, above-mentioned hydrogen peroxide, formic acid and sulfuric acid part add for three times, after epoxy reaction finishes, and standing demix, the sour water of lower floor is told, add the alkali rear recycling that neutralizes, upper solution is put into dehydration tower, obtains thick epoxy aliphatic acid methyl ester after sloughing moisture content.
(4) above-mentioned thick epoxy aliphatic acid methyl ester is carried out the epoxy aliphatic acid methyl ester that three grades of rectifying obtain three kinds of models:
One-level rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 1:1;
Two-stage rectification: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 3:1;
Three grades of rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 6:1;
Above-mentioned three grades of rectifying can obtain respectively the epoxy aliphatic acid methyl ester of three kinds of models, and described three kinds of models are to classify by the difference of carbon content, and its physical properties index sees Table 1.
The physicals of the epoxy aliphatic acid methyl ester of three kinds of models that three grades of rectifying of table 1 obtain
| Model | Oxirane value | Acid number | Color (platinum cobalt colorimetric) | Density | Condensation point | Smell | Flash-point |
| 1# | 5.0 | 0.2 | 40 | 0.945 | 7℃ | Nothing | 182℃ |
| 2# | 4.8 | 1.1 | 150 | 0.95 | 4℃ | Nothing | 190℃ |
| 3# | 4.0 | 1.2 | 125 | 0.928 | 5℃ | Have | 170℃ |
Described 1# epoxy aliphatic acid methyl ester is applied to the softening agent of high-end PVC product; 2# and 3# epoxy aliphatic acid methyl ester are applied to low and middle-end PVC product such as electric wire, sheet material, tubing, the softening agent of plastics shoes, refrigerator sealed strip etc.
Embodiment 2
(1) by weight percentage the sulfuric acid of 97% sewer oil and 3% is added in the reactor, be heated to 75-85 ℃, drip methyl alcohol and carry out esterification, methyl alcohol rate of addition 150kg/h, methanol usage is sewer oil 160kg per ton, reaction times 10h, simultaneously recovery steams condensed methyl alcohol and puts into the use of methanol rectifying tower Recovery and recycle, after reaction finishes, tell the glycerine of lower floor, add in the sodium hydroxide of its weight 6% in the supernatant liquid and unnecessary sulfuric acid, standing demix again, the upper strata is crude fatty acid methyl ester;
(2) crude fatty acid methyl ester that obtains in the step (1) is carried out the molecule rectification and purification, distillation temperature is 200-220 ℃, and vacuum tightness is 0.1-10Pa, isolates colloid and plant asphalt, the fatty acid methyl ester that obtains purifying;
(3) fatty acid methyl ester after step (2) purification is squeezed into reactor, the hydrogen peroxide, 10% formic acid and 8% the sulfuric acid that add its weight 32%, under 75-85 ℃, 7-10Pa pressure-fired, stir and carried out epoxidation reaction in 14 hours, above-mentioned hydrogen peroxide, formic acid and sulfuric acid part add for three times, after epoxy reaction finishes, and standing demix, the sour water of lower floor is told, add the alkali rear recycling that neutralizes, upper solution is put into dehydration tower, obtains thick epoxy aliphatic acid methyl ester after sloughing moisture content.
(4) above-mentioned thick epoxy aliphatic acid methyl ester is carried out three grades of rectifying to purify, the condition of three grades of rectifying is with embodiment 1.
Embodiment 3
(1) by weight percentage the sulfuric acid of 99.8% sewer oil and 0.2% is added in the reactor, be heated to 75-85 ℃, drip methyl alcohol and carry out esterification, methyl alcohol rate of addition 200kg/h, methanol usage is sewer oil 140kg per ton, reaction times 9h, simultaneously recovery steams condensed methyl alcohol and puts into the use of methanol rectifying tower Recovery and recycle, after reaction finishes, tell the glycerine of lower floor, add in the sodium hydroxide of its weight 8% in the supernatant liquid and unnecessary sulfuric acid, standing demix again, the upper strata is crude fatty acid methyl ester;
(2) crude fatty acid methyl ester that obtains in the step (1) is carried out the molecule rectification and purification, distillation temperature is 200-220 ℃, and vacuum tightness is 0.1-10Pa, isolates colloid and plant asphalt, the fatty acid methyl ester that obtains purifying;
(3) fatty acid methyl ester after step (2) purification is squeezed into reactor, the hydrogen peroxide, 6% formic acid and 10% the sulfuric acid that add its weight 30%, under 75-85 ℃, 7-10Pa pressure-fired, stir and carried out epoxidation reaction in 13 hours, above-mentioned hydrogen peroxide, formic acid and sulfuric acid part add for three times, after epoxy reaction finishes, and standing demix, the sour water of lower floor is told, add the alkali rear recycling that neutralizes, upper solution is put into dehydration tower, obtains thick epoxy aliphatic acid methyl ester after sloughing moisture content.
(4) above-mentioned thick epoxy aliphatic acid methyl ester is carried out three grades of rectifying to purify, the condition of three grades of rectifying is with embodiment 1.
Claims (2)
1. a method of producing epoxy aliphatic acid methyl ester with sewer oil is characterized in that it comprises the steps:
(1) by weight percentage the sewer oil of 95-99.8% and the sulfuric acid of 0.2-5% are added in the reactor, be heated to 75-85 ℃, drip methyl alcohol and carry out esterification, methyl alcohol rate of addition 150-200kg/h, methanol usage is sewer oil 120-160kg per ton, reaction times 8-10h after reaction finishes, tells the glycerine of lower floor, add in the sodium hydroxide of its weight 5-8% in the supernatant liquid and unnecessary sulfuric acid, standing demix again, the upper strata is crude fatty acid methyl ester, is isolated out stand-by;
(2) crude fatty acid methyl ester that obtains in the step (1) is carried out the molecule rectification and purification, distillation temperature is 200-220 ℃, and vacuum tightness is 0.1-10Pa, isolates colloid and plant asphalt, the fatty acid methyl ester that obtains purifying;
(3) fatty acid methyl ester after step (2) purification is squeezed into reactor, add the hydrogen peroxide of its weight 30-35%, the formic acid of 6-10% and the sulfuric acid of 5-10%, under 75-85 ℃, 3-7Pa, stir and carried out epoxidation reaction in 12-14 hour, after epoxy reaction finishes, standing demix is told the sour water of lower floor, adds the alkali rear recycling that neutralizes, upper solution is put into dehydration tower, obtains thick epoxy aliphatic acid methyl ester after sloughing moisture;
(4) the thick epoxy aliphatic acid methyl ester that obtains in the step (3) is carried out the epoxy aliphatic acid methyl ester that three grades of rectifying obtain three kinds of models.
2. a kind of method of producing epoxy aliphatic acid methyl ester with sewer oil according to claim 1 is characterized in that the condition of described three grades of rectifying is respectively:
One-level rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 1:1;
Two-stage rectification: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 3:1;
Three grades of rectifying: 200 ℃ of temperature, vacuum tightness 0.1-10Pa, reflux ratio 6:1.
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| CN 201110072671 CN102161938B (en) | 2011-03-25 | 2011-03-25 | Method for producing epoxy fatty acid methyl ester by using illegal cooking oil |
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| CN 201110072671 CN102161938B (en) | 2011-03-25 | 2011-03-25 | Method for producing epoxy fatty acid methyl ester by using illegal cooking oil |
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| CN102161938B true CN102161938B (en) | 2013-01-02 |
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| CN102993132B (en) * | 2012-12-07 | 2014-12-31 | 浙江工业大学 | Device for producing epoxidized fatty acid methyl ester |
| CN103172851A (en) * | 2013-03-21 | 2013-06-26 | 安徽理工大学 | Method for preparing polyglycerol fatty acid ester with illegal cooking oil |
| CN103193933B (en) * | 2013-03-29 | 2015-07-08 | 宁波市江北成达色母粒有限公司 | Preparation method of macromolecule plasticizer based on recycled cooking oil |
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| CN103773609A (en) * | 2013-10-29 | 2014-05-07 | 尚诚德 | Method for preparing plastic plasticizer by using illegally recycled waste cooking oil |
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| CN104557796B (en) * | 2015-01-21 | 2016-06-29 | 吴俊荣 | The preparation method of epoxy aliphatic acid methyl ester |
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| CN104592170A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Method for producing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100580025C (en) * | 2007-02-27 | 2010-01-13 | 张伟明 | Method for producing epoxy plasticizer from dirty oil and vegetable and animal waste oil |
| CN100590188C (en) * | 2007-05-22 | 2010-02-17 | 江阴市向阳科技有限公司 | Method for producing epoxy plasticizer using waste grease |
| CN101372539B (en) * | 2008-07-31 | 2011-07-06 | 浙江嘉澳环保科技股份有限公司 | Method for producing environment-friendly type plasticiser using waste oil and oil foot |
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Owner name: HEBEI JINGU PLASTICISER CO., LTD. Free format text: FORMER OWNER: HEBEI JINGU GREASE TECHNOLOGY CO., LTD. Effective date: 20131205 |
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Effective date of registration: 20131205 Address after: 052360 Song Cun, king of the heavenly palace camp in Xinji, Hebei, Shijiazhuang Patentee after: Hebei Jingu plasticizer Co.,Ltd. Address before: 052360 Song Cun, king of the heavenly palace camp in Xinji, Hebei, Shijiazhuang Patentee before: HEBEI JINGU GREASE TECHNOLOGY Co.,Ltd. |
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