CN1775936A - Oleic clean-production method - Google Patents
Oleic clean-production method Download PDFInfo
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- CN1775936A CN1775936A CN 200510095546 CN200510095546A CN1775936A CN 1775936 A CN1775936 A CN 1775936A CN 200510095546 CN200510095546 CN 200510095546 CN 200510095546 A CN200510095546 A CN 200510095546A CN 1775936 A CN1775936 A CN 1775936A
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- butanols
- water
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- urea
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Abstract
The invention relates to a method to make oleic acid using mixture fatty acid hydrolyzed from propagation grease. It includes the following steps: mixing the mixture fatty acid with butanol, carbamide, and water; crystallizing; cooling the mixture and filtering; debagging. The invention is the improvement to classic carbamide envelope separating method. It adopts butanol-carbamide-water system to separate fatty acid and the solution and carbamide could be recycled to use. Thus, there is no pollution to release.
Description
Technical field
The present invention relates to a kind of mixed fatty acid with the animal-plant oil hydrolysis is raw material, prepares oleic method.
Background technology
Industrial fatty acid is mainly derived from grease.The weight of lipid acid in grease accounts for 90%, and the natural animal-plant grease is the mixture of different triglyceride, and it is identical that the acyl group of three lipid acid in the Witepsol W-S 55 has, the difference that has.Grease is made mixed fatty acid by hydrolysis.Oleic acid wherein is a kind of very important fine chemical product, and it is used for synthetic detergent, coating, plastics, makeup, food emulsifier, lubricant, mineral flotation agent, rubber batching, superpolymer emulsifying agent, pharmaceutical preparation etc.
Because oleic acid content is 30～50% in general animal-plant oil such as tallow, lard, peanut oil, the soybean oil, such mixed fatty acid often is not suitable as the application requiring of industrial oleic acid, so need such mixed fatty acid is separated.At present, the separation method at industrial lipid acid has branch to coil freezing milling process, hydrophily partition method (claiming the tensio-active agent partition method again), temp controlled vessel crystallization process, rectifying separation method, solvent separation, urea clathrate partition method etc.In the urea clathrate partition method, often add methyl alcohol or alcohol solvent and urea, though separation efficiency is higher, a large amount of aqueous solution of urea dischargings is arranged after separating, solvent easily loses simultaneously.
Summary of the invention
The objective of the invention is to invent the oleic clean preparation method of a kind of nothing " three wastes " discharging.
The present invention includes following steps:
1) inclusion: mixed fatty acid and butanols, urea, the water of Vegetable oil lipoprotein hydrolysis are mixed;
2) crystallization: mixture is cooled off, filter then, tell solid phase I and liquid phase I;
3) unpack: add water in solid phase I, the pyrolysis bag is told oil phase and water;
4) recrystallize: liquid phase I is mixed with butanols, urea; Cooling mixed liquid filters, and tells solid phase II and liquid phase II;
5) unpack: add water in solid phase II, the pyrolysis bag is told oil phase and water, and oil phase is an oleic acid again.
The present invention is the improvement to traditional urea clathrate partition method, adopts butanols-urea-water inclusion system, and separation of fatty acids all reclaims repeated use with solvent in the sepn process and urea, does not have " three wastes " discharging, realizes cleaner production.
Above-mentioned butanols can be propyl carbinol, also can be isopropylcarbinol.
Temperature when cooling step 2 of the present invention) and filtration is respectively 5～15 ℃.
Temperature when cooling in the step 4) and filtration is respectively-10～0 ℃.
Earlier that butanols is soluble in water in the step 1), mix with urea, mixed fatty acid again after being made into the butanols aqueous solution, the mass ratio of butanols and water is 20: 1～2 in the butanols aqueous solution.
The mass ratio of the mixed fatty acid and the butanols aqueous solution, urea is 1: 2～8: 0.5～1.3 in the step 1).
The liquid phase II underpressure distillation of step 4) is gone out butanols, the butanols that obtains reclaiming.
With step 2) and 4) solid matter add the hydrolysis bag after, water is mixed with butanols, through underpressure distillation, separate and also to reclaim butanols, water, butanols and urea mixed solution respectively.
Butanols and urea mixed solution are added step 2) in liquid phase I in.
In the mixed solution in the butanols adding step 1) that reclaims.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Specific embodiment
Embodiment one
The raw material mixed fatty acid is that animal-plant oil passes through ordinary method (high-pressure decomposing method) hydrolysis and gets, and it consists of: saturated fatty acid is 15.8%, and oleic acid is 44.0%, and polyene unsaturated fatty acid is 40.2%.The composition of lipid acid is by gas chromatography determination, and used butanols comprises propyl carbinol and isopropylcarbinol, and example 1～3 is a propyl carbinol, and example 4～6 is an isopropylcarbinol.
Get the 4000g butanols aqueous solution (mass ratio of fourth alcohol and water is 20: 1～2) and 500g urea, stirring is fully dissolved it under 70 ℃, or adds the butanols-urea-aqueous solution of the respective quality composition that reclaims.Add the 1000g mixed fatty acid again, stir under 50r/min then, with the speed of cooling of 10 ℃/h, feed liquid is reduced to 20 ℃ from 70 ℃, with the speed of cooling of 5 ℃/h, feed liquid is reduced to the cold temperature of I (5～15 ℃) then, insulation 1h filters and tells solid phase I and liquid phase I.
Solid phase I is saturated fatty acid-urea inclusion, adds 2 times of water to the solid phase quality, or through the water that underpressure distillation is told, is heated to 80 ℃ and unpacks, and tells oil phase I and water I.
Oil phase I is that saturated fatty acid (stearic acid, palmitinic acid) water I is urea-aqueous solution, processing to be recycled.
Liquid phase I is unsaturated fatty acids-butanols liquid, in liquid phase I, add Mg butanols-urea (butanols and urea quality ratio are 5: 1) again, be heated to 50 ℃, under 50r/min, stir then,, feed liquid is reduced to 20 ℃ from 50 ℃ with the speed of cooling of 10 ℃/h, then with the speed of cooling of 5 ℃/h, feed liquid is reduced to the cold temperature of II (10～0 ℃), and insulation 1h filters and tells solid phase II and liquid phase II.
Solid phase II is oleic acid-urea inclusion, adds 2 times of water to the solid phase quality, or through the water that underpressure distillation is told, is heated to 70 ℃ and unpacks, and tells oil phase II and water II.
Water II is urea-aqueous solution, and oil phase II promptly gets oleic acid through washing dehydration.
Liquid phase II is polyene fatty acid-butanols liquid, and through underpressure distillation, still liquid is polyene fatty acid (linolic acid, linolenic acid etc.), and the butanols that steams is reused for the urine inclusion and mixes with water II.
Water I and water II and butanols are mixed mutually, and mixed solution steams butanols-water azeotrope, the cut AUTOMATIC ZONING through underpressure distillation, tell the fourth alcohol and water, butanols is reused for the urine inclusion, and water is used for the pyrolysis bag, still liquid is butanols-urea, and a part is returned the urine inclusion, and a part is added among the liquid phase I.
Component, output and the extraction yield of concrete separation condition and oleic acid product are as shown in table 1.
Table 1
| Embodiment | Separation condition | The component of oleic acid product and output | ||||||
| The cold temperature of I/℃ | M/g | The cold temperature of II/℃ | Saturated fatty acid content/% | Oleic acid content/% | Polyene unsaturated fatty acid content/% | Oleic acid output/g | The oleic acid extraction yield */％ | |
| 1 | 10 | 1000 | -5 | 5.4 | 72.1 | 22.5 | 366 | 60.0 |
| 2 | 7 | 2000 | -5 | 4.5 | 75.6 | 19.9 | 382 | 65.6 |
| 3 | 10 | 2000 | -8 | 5.4 | 65.2 | 29.4 | 484 | 71.7 |
| 4 | 13 | 3000 | -2 | 9.1 | 75.2 | 15.7 | 433 | 74.0 |
| 5 | 10 | 4000 | -2 | 6.1 | 79.5 | 14.4 | 442 | 79.9 |
| 6 | 7 | 4000 | -5 | 4.7 | 73.7 | 21.6 | 426 | 71.4 |
*Oleic acid extraction yield=(in the product in pure oleic acid amount/mixed fatty acid contained oleic acid amount) * 100%
All repeated to use the butanols, urea and the water that reclaim in an embodiment, the rate of recovery of butanols is 92%, and the rate of recovery of urea is 95%, and required butanols, urea amount insufficient section in sepn process replenish realization by fresh material.
Embodiment two
The example of different mass ratio between the 1000g and the butanols aqueous solution, urea, operation steps is with embodiment one, and the result is as shown in table 2.Butanols in the example 7～9 is a propyl carbinol.
Table 2
| Embodiment | Mixed fatty acid: the butanols aqueous solution (mass ratio) | Mixed fatty acid: urea (mass ratio) | The cold temperature of I/℃ | M/g | The cold temperature of II/℃ | Oleic acid content/% | Oleic acid extraction yield/% |
| 7 | 1∶2 | 1∶0.5 | 5 | 2000 | -3 | 77.3 | 64.1 |
| 8 | 1∶4 | 1∶1.0 | 10 | 1000 | -10 | 70.4 | 81.5 |
| 9 | 1∶8 | 1∶1.3 | 15 | 500 | 0 | 73.0 | 58.6 |
Claims (10)
1, a kind of oleic clean preparation method is characterized in that may further comprise the steps:
1) inclusion: mixed fatty acid and butanols, urea, the water of Vegetable oil lipoprotein hydrolysis are mixed;
2) crystallization: mixture is cooled off, filter then, tell solid phase I and liquid phase I;
3) unpack: add water in solid phase I, the pyrolysis bag is told oil phase and water;
4) recrystallize: liquid phase I is mixed with butanols, urea; Cooling mixed liquid filters, and tells solid phase II and liquid phase II;
5) unpack: add water in solid phase II, the pyrolysis bag is told oil phase and water, and oil phase is an oleic acid again.
2,, it is characterized in that described butanols is propyl carbinol or isopropylcarbinol according to the described oleic clean preparation method of claim 1.
3, according to the described oleic clean preparation method of claim 1, it is characterized in that step 2) in cooling and the temperature when filtering be respectively 5～15 ℃.
4,, it is characterized in that the cooling in the step 4) and the temperature when filtering is respectively-10～0 ℃ according to the described oleic clean preparation method of claim 1.
5, according to the described oleic clean preparation method of claim 1, it is characterized in that in the step 1) earlier that butanols is soluble in waterly, mix with mixed fatty acid, urea again after being made into the butanols aqueous solution, the mass ratio of butanols and water is 20: 1～2 in the butanols aqueous solution.
6,, it is characterized in that the mass ratio of mixed fatty acid and the butanols aqueous solution in the step 1), urea is 1: 2～8: 0.5～1.3 according to the described oleic clean preparation method of claim 5.
7,, it is characterized in that the liquid phase II underpressure distillation of step 4) being gone out butanols, the butanols that obtains reclaiming according to the described oleic clean preparation method of claim 1.
8, according to the described oleic clean preparation method of claim 1, it is characterized in that step 2) and 4) solid matter add the hydrolysis bag after, water is mixed with butanols, through underpressure distillation, separate and also to reclaim butanols, water, butanols and urea mixed solution respectively.
9, described according to Claim 8 oleic clean preparation method is characterized in that butanols and urea mixed solution are added step 2) in liquid phase I in.
10, according to claim 7 or 8 described oleic clean preparation methods, in the mixed solution in the butanols adding step 1) that it is characterized in that to reclaim.
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| CN 200510095546 CN100335602C (en) | 2005-11-18 | 2005-11-18 | Oleic clean-production method |
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| CN 200510095546 CN100335602C (en) | 2005-11-18 | 2005-11-18 | Oleic clean-production method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838590A (en) * | 2010-05-25 | 2010-09-22 | 九江力山环保科技有限公司 | Production process of rectified light-colored oleic acid |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN103864603A (en) * | 2012-12-12 | 2014-06-18 | 上海晶纯实业有限公司 | Purifying method of highly pure oleic acid |
| CN104668102A (en) * | 2015-03-10 | 2015-06-03 | 云南磷化集团有限公司 | Obverse flotation collecting agent for low temperature-resistant collophanite and preparation method thereof |
| CN105566167A (en) * | 2014-10-17 | 2016-05-11 | 浙江医药股份有限公司新昌制药厂 | Method for recovering urea in urea inclusion process |
-
2005
- 2005-11-18 CN CN 200510095546 patent/CN100335602C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838590A (en) * | 2010-05-25 | 2010-09-22 | 九江力山环保科技有限公司 | Production process of rectified light-colored oleic acid |
| CN101845362A (en) * | 2010-06-22 | 2010-09-29 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN101845362B (en) * | 2010-06-22 | 2012-07-25 | 中南林业科技大学 | Method for gathering oleic acid from tea-seed oil |
| CN103864603A (en) * | 2012-12-12 | 2014-06-18 | 上海晶纯实业有限公司 | Purifying method of highly pure oleic acid |
| CN105566167A (en) * | 2014-10-17 | 2016-05-11 | 浙江医药股份有限公司新昌制药厂 | Method for recovering urea in urea inclusion process |
| CN105566167B (en) * | 2014-10-17 | 2018-04-03 | 浙江医药股份有限公司新昌制药厂 | The recovery method of urea in a kind of urea job contract skill |
| CN104668102A (en) * | 2015-03-10 | 2015-06-03 | 云南磷化集团有限公司 | Obverse flotation collecting agent for low temperature-resistant collophanite and preparation method thereof |
| CN104668102B (en) * | 2015-03-10 | 2017-08-04 | 云南磷化集团有限公司 | A kind of low temperature resistant Cellophane direct flotation collecting agent and preparation method thereof |
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|---|---|
| CN100335602C (en) | 2007-09-05 |
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