CN107311854B - Preparation method of solid powdery potassium oleate - Google Patents
Preparation method of solid powdery potassium oleate Download PDFInfo
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- CN107311854B CN107311854B CN201710600443.8A CN201710600443A CN107311854B CN 107311854 B CN107311854 B CN 107311854B CN 201710600443 A CN201710600443 A CN 201710600443A CN 107311854 B CN107311854 B CN 107311854B
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- potassium oleate
- urea
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- solid
- alcohol
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- 229940096992 potassium oleate Drugs 0.000 title claims abstract description 64
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 title claims abstract description 64
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004202 carbamide Substances 0.000 claims abstract description 29
- 235000011837 pasties Nutrition 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005642 Oleic acid Substances 0.000 claims abstract description 13
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 13
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- 230000009969 flowable effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- MLGZWBPQUONOQV-UHFFFAOYSA-M potassium (Z)-octadec-9-enoate hydrate Chemical compound [OH-].[K+].C(CCCCCCCC=C/CCCCCCCC)(=O)O MLGZWBPQUONOQV-UHFFFAOYSA-M 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of solid powdery potassium oleate, which comprises the steps of reacting pasty oleic acid with potassium hydroxide in a water phase to prepare a potassium oleate solution, and concentrating at 70-80 ℃ to prepare flowable viscous potassium oleate; mixing urea and an alcohol solution, stirring at 70-90 ℃, and forming a hot saturated urea-alcohol solution after the urea is completely dissolved; adding viscous potassium oleate into the urea-alcohol solution under the condition of heat preservation, fully stirring to form a uniform transparent solution, keeping stirring and cooling to-5-0 ℃, keeping the low temperature for 1-3h to separate out the potassium oleate, filtering the separated hard potassium oleate powder, and drying the solid by dry cold air to obtain the finished product of solid powdery potassium oleate. The invention utilizes a urea inclusion method to prepare high-purity solid powdery potassium oleate which contains almost no moisture, utilizes the excellent water solubility of urea and alcohol and the volatility of alcohol, and uses saturated urea-alcohol solution to absorb the moisture in the potassium oleate to finally obtain the solid loose powdery potassium oleate.
Description
Technical Field
The invention belongs to the technical field of preparation of potassium oleate, and particularly relates to a preparation method of solid powdery potassium oleate.
Background
Potassium oleate is usually prepared in the aqueous phase by saponification using animal or vegetable oils containing the oleic acid component. The potassium oleate products respectively comprise a potassium oleate solution (the content of potassium oleate is lower than 30%) which is colorless to light yellow viscous liquid, pasty potassium oleate (the content of potassium oleate is 50%) which is light yellow to light brown viscous silk liquid, pasty potassium oleate (the content of potassium oleate is 70% -92%) which is light yellow soft pasty solid and potassium oleate particles (the content of potassium oleate is higher than 95%) which are light yellow powdery particles due to different mass contents of potassium oleate. Potassium oleate is a potassium catalyst, is a trimerization catalyst of polyurethane rigid polyisocyanurate, and is widely used in PIR foam systems of polyurethane insulation boards. In addition, the potassium oleate is widely applied to the fields of rubber emulsifying agents, foaming agents, isolating agents, cleaning agents, lubricating agents, fiber softening agents, surfactants and the like. The potassium oleate solution has the defects of low effective content, inconvenient transportation, storage and packaging and the like, and certain high-concentration potassium oleate solution often needs to be added with auxiliary agents such as viscosity reducer, dispersant and the like in use due to large water content, so the application field is further limited; the contents of effective components of the pasty potassium oleate and the pasty potassium oleate are high. However, the viscosity is high, and potassium oleate in the product is easy to agglomerate at low temperature, so that the application is inconvenient, for example, the taking amount is not easy to be controlled in use, and the filling and taking are inconvenient. Compared with the two, the high-purity potassium oleate is powdery solid, and brings great convenience in storage, packaging and transportation and taking during use. However, the existing solid potassium oleate refining and purifying usually needs to adopt a low-temperature decompression mode to remove moisture, and the method has the advantages of long production period, high energy consumption, higher cost and great preparation difficulty. Therefore, research and development on the preparation process of the solid potassium oleate are necessary.
The invention content is as follows:
the invention solves the technical problem of providing a simple and convenient-to-operate preparation method of solid powdery potassium oleate. The method utilizes a urea inclusion method to prepare the solid powdery potassium oleate with high purity and almost no moisture. By utilizing the excellent water solubility of urea and alcohol and the volatility of alcohol, saturated urea-alcohol solution is used for absorbing the water in the potassium oleate to finally obtain the solid loose powdery potassium oleate.
The invention adopts the following technical scheme for solving the technical problems:
a preparation method of solid powdery potassium oleate comprises the following specific steps:
(1) reacting the pasty oleic acid with potassium hydroxide in an aqueous phase to prepare a potassium oleate solution with the mass content of 10-20%, and concentrating at 70-80 ℃ to prepare flowable viscous potassium oleate with the mass content of 40-60%;
(2) mixing urea and an alcohol solution, stirring at 70-90 ℃, and forming a hot saturated urea-alcohol solution after the urea is completely dissolved;
(3) adding viscous potassium oleate into the urea-alcohol solution under the condition of heat preservation, fully stirring to form a uniform transparent solution, keeping stirring, cooling the solution to-5-0 ℃, keeping the temperature for 1-3h to separate out potassium oleate solids, filtering the separated hard potassium oleate powder (filtering with fine gauze), and drying the solids with dry cold air to obtain the finished product of solid powdery potassium oleate.
Further preferably, the alcohol solution is one or more of a methanol solution, an ethanol solution or an isopropanol solution, wherein the purity of the methanol solution, the ethanol solution or the isopropanol solution is higher than 95%.
More preferably, the mass ratio of the urea to the viscous potassium oleate is 1.3:1, and the mass ratio of the volume of the alcoholic solution to the urea is 1mL:2.4 g.
More preferably, the alcohol in the filtered filtrate can be recovered and reused after distillation, and the urea can be recovered and reused after recrystallization. The cost for preparing the potassium oleate is reduced.
The invention uses the strong water absorption of the hot saturated urea-alcohol solution during cooling to efficiently capture the water in the potassium oleate-water mixture, and uses the principle that the separated minimum amount of urea can include the potassium oleate to form stable crystals.
According to the urea inclusion method, the high-water-solubility urea has little residue in the potassium oleate powder, so that a product with high purity and almost no moisture can be obtained, and the prepared potassium oleate powder is subjected to very little urea inclusion, is not sticky on the surface and is not easy to cake, so that the potassium oleate powder is more convenient and quicker to package, store, take and the like.
The alcohol solution used in the process of preparing the potassium oleate can be recycled by simple distillation, the urea can be recycled by recrystallization, the whole preparation process almost has no generation of industrial three wastes, the green chemical concept is met, the investment on equipment and raw materials used in the preparation process is low, the benefit is fast, and the method is favorable for industrial popularization and application.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Examples
The raw materials are respectively weighed according to the following mixture ratio:
1. 50Kg of pasty oleic acid, 9Kg of potassium hydroxide, 300L of deionized water, 120Kg of urea and 300L of ethanol solution;
2. 60Kg of pasty oleic acid, 12Kg of potassium hydroxide, 300L of deionized water, 150Kg of urea and 300L of isopropanol solution;
3. 100Kg of pasty oleic acid, 20Kg of potassium hydroxide, 600L of deionized water, 300Kg of urea and 600L of methanol solution;
4. 50Kg of pasty oleic acid, 9Kg of potassium hydroxide, 300L of deionized water, 120Kg of urea and 480L of ethanol solution.
The production method comprises the following steps:
1. weighing the raw materials according to the proportion, heating deionized water, adding potassium hydroxide and pasty oleic acid, fully dissolving to obtain 10-20% by mass of potassium oleate colloidal liquid, heating to 70-80 ℃, and concentrating to prepare 40-60% by mass of viscous potassium oleate;
2. heating the alcohol solution, adding urea to fully dissolve, and then refluxing and heating to 80 ℃ to form a hot saturated urea-alcohol solution; 3. adding viscous potassium oleate into hot saturated urea-alcohol solution under heat preservation, stirring, distilling to remove 20% solvent, cooling hot solution to-5 deg.C, and maintaining low temperature for 1-3 hr to separate out a large amount of solid.
4. Filtering solid with fine gauze, centrifuging the solid in a drum centrifuge to obtain solid potassium oleate with purity higher than 95%, or further refining to obtain solid potassium oleate with higher specification.
5. And distilling the alcohol in the liquid phase component, and then recycling the alcohol, and recrystallizing the urea, and then recycling the urea.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. A preparation method of solid powdery potassium oleate is characterized by comprising the following specific steps:
(1) respectively weighing the raw materials according to any one of the following a-d proportions:
a, proportioning: 50kg of pasty oleic acid, 9kg of potassium hydroxide, 300L of deionized water, 120kg of urea and 300L of ethanol solution;
b, proportioning: 60kg of pasty oleic acid, 12kg of potassium hydroxide, 300L of deionized water, 150kg of urea and 300L of isopropanol solution;
c, proportioning: 100kg of pasty oleic acid, 20kg of potassium hydroxide, 600L of deionized water, 300kg of urea and 600L of methanol solution;
d, proportioning: 50kg of pasty oleic acid, 9kg of potassium hydroxide, 300L of deionized water, 120kg of urea and 480L of ethanol solution;
weighing the raw materials according to the proportion, heating deionized water, adding potassium hydroxide and pasty oleic acid, fully dissolving to obtain potassium oleate colloidal liquid, heating to 70-80 ℃, and concentrating to prepare viscous potassium oleate with the mass content of 40% -60%;
(2) heating the alcohol solution, adding urea to fully dissolve, and then refluxing and heating to 80 ℃ to form a hot saturated urea-alcohol solution;
(3) adding viscous potassium oleate into hot saturated urea-alcohol solution under heat preservation, stirring, distilling to remove 20% solvent, cooling hot solution to-5 deg.C, and maintaining low temperature for 1-3 hr to separate out a large amount of solid; filtering out solid with fine gauze, centrifuging the solid in a drum centrifuge to obtain solid potassium oleate with purity higher than 95%, distilling alcohol in liquid phase component, recovering alcohol, and recrystallizing urea.
2. The method of preparing solid powdery potassium oleate according to claim 1, characterized in that: the purity of the methanol solution, the ethanol solution or the isopropanol solution is higher than 95 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710600443.8A CN107311854B (en) | 2017-07-21 | 2017-07-21 | Preparation method of solid powdery potassium oleate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710600443.8A CN107311854B (en) | 2017-07-21 | 2017-07-21 | Preparation method of solid powdery potassium oleate |
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| Publication Number | Publication Date |
|---|---|
| CN107311854A CN107311854A (en) | 2017-11-03 |
| CN107311854B true CN107311854B (en) | 2020-03-10 |
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| CN201710600443.8A Active CN107311854B (en) | 2017-07-21 | 2017-07-21 | Preparation method of solid powdery potassium oleate |
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| Country | Link |
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| CN (1) | CN107311854B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106831409A (en) * | 2017-03-07 | 2017-06-13 | 辽宁奥克医药辅料股份有限公司 | A kind of preparation method of high-purity oleic acid |
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2017
- 2017-07-21 CN CN201710600443.8A patent/CN107311854B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106831409A (en) * | 2017-03-07 | 2017-06-13 | 辽宁奥克医药辅料股份有限公司 | A kind of preparation method of high-purity oleic acid |
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| Publication number | Publication date |
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| CN107311854A (en) | 2017-11-03 |
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