CN109053639B - Continuous production method for epoxidation of grease - Google Patents
Continuous production method for epoxidation of grease Download PDFInfo
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- CN109053639B CN109053639B CN201810827249.8A CN201810827249A CN109053639B CN 109053639 B CN109053639 B CN 109053639B CN 201810827249 A CN201810827249 A CN 201810827249A CN 109053639 B CN109053639 B CN 109053639B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Abstract
The invention discloses a continuous production method for epoxidation of grease, which takes unsaturated grease and hydrogen peroxide as raw materials, formic acid as a catalyst, PEG-30 as an oil-water dispersant, a hydrodynamic cavitation element as a mixer, reaction liquid realizes oil-water two-phase mixing through the hydrodynamic cavitation element, and the mixed reaction liquid is subjected to continuous epoxidation reaction in a heat exchange type reactor to obtain epoxy grease. According to the invention, only a very small amount of PEG-30 needs to be added in the reaction process, so that the PEG-30 and the hydrodynamic cavitation technology are coupled to strengthen the initial mixing of oil and water phases, and the good mixing state is continuously maintained in the subsequent reaction, therefore, a continuous production mode can be realized, the production efficiency is high, and the quality of the final epoxy grease product is not influenced by the addition of the PEG-30; the process can realize large-scale industrial production and has low production cost.
Description
Technical Field
The invention relates to a continuous production method for epoxidation of grease.
Background
The epoxidation reaction system of the grease belongs to a liquid-liquid heterogeneous strong exothermic reaction system, and good mass transfer and heat transfer are the precondition for ensuring the smooth proceeding of the reactions. The realization of continuous production can greatly reduce the production cost and improve the production safety.
Currently, mechanically stirred reactors are mostly adopted for the alicyclic oxidation in industry (Chinese patents CN 201482479U, CN101914219B CN102391210A, CN 101139328B, CN 101284821A, CN 100580025C, CN100590188C, CN 101928267B and CN 102675254A). (1) The reactor realizes the mixing of materials by means of the stirring paddle, and the liquid is easy to form small circulation locally in the stirring process, so that the oil-water two-phase contact is insufficient, and the reaction efficiency is low. The reaction which needs to be completed in a laboratory within about 8 hours under the condition of the same material proportion is completed in 12-16 hours in an industrial stirring reactor, which fully explains the importance of mixing for the reaction. (2) In a mechanical stirring reactor, the heat exchange of materials is mainly realized by a coil immersed in the materials. However, the heat release amount of the epoxidation of the grease is as high as 60kcal/mol, and the immersion heat exchange heat transfer coefficient is low, so that the requirement of a reactor for heat transfer is far from being met. In general, the temperature is prevented from rising too high by adding hydrogen peroxide slowly (2-4 hours of adding time), but the temperature fluctuation still exceeds 10 ℃, so that the product quality is affected, and meanwhile, a great potential safety hazard is brought. (3) In addition, the stirring structure is adopted, the larger the reaction tank is, the higher the stirring power is, the industrial amplification is not facilitated, and the lower the economical efficiency of the stirring reactor is reflected.
In order to enhance the mixing effect, epoxidation reactors of different structures have also been proposed in the prior art.
Chinese patent CN 102993132 proposes a technology for producing epoxy fatty acid methyl ester by using hydrodynamic cavitation technology, and the material mixing is realized by using cavitation effect. Cavitation achieves good initial mixing of the oil and water phases, however the device has no corresponding structure to maintain good mixing, and droplets coalesce and cause poor subsequent mixing. In addition, the device still adopts the structure of immersive heat transfer, and the reaction temperature of oil alicyclic ring oxidation can not be stably controlled. Chinese patent CN104962396 proposes an external circulation grease epoxidation reaction kettle. The mixing of oil and water is realized through the emulsification dispersion device arranged on the external circulation, and the heat exchange is realized by the jacket of the reaction kettle. Obviously, it still does not solve the two problems of maintaining the oil-water dispersion state and good heat exchange well. Chinese patent CN 105561893 proposes a grease epoxidation reaction apparatus coupling hydrodynamic cavitation and a tubular reactor. The apparatus still suffers from the problem that good mixing cannot be maintained for a long period of time, and the epoxidation reaction usually takes more than 1 hour, and therefore, remains in a batch mode of production.
Although the initial mixing of oil and water is realized through the hydrodynamic cavitation technology and the emulsification and dispersion device, the initial mixing of the oil and the water can only be realized, the oil and the water can be quickly layered, the oil and the water cannot be kept in a good mixing state, and the intermittent production mode is adopted, so that the production efficiency is low.
In the prior art, a continuous production mode capable of realizing epoxidation reaction is available, but the production cost is high. The literature (Model for a Cascade Continuous oxidation Process, JAOCS, Vol. 76, No. 1(1999), 89-92) proposes a Continuous production method: the continuous production of the epoxidation of the grease is realized by the multistage series connection of a plurality of stirred tank reactors. However, the multi-kettle series mode equipment is complex, the equipment amount is large, the investment is large, the occupied area is large, and a large amount of equipment also puts higher requirements on control and safety.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a continuous production method for epoxidation of fats, which has simple process and apparatus structure and low energy consumption and production cost.
The continuous production method for the epoxidation of the grease is characterized in that unsaturated grease and hydrogen peroxide are used as raw materials, formic acid is used as a catalyst, PEG-30 is used as an oil-water dispersing agent, a hydrodynamic cavitation element is used as a mixer, the raw materials, the catalyst and the oil-water dispersing agent are mixed by the hydrodynamic cavitation element to realize oil-water two-phase mixing, and the mixed reaction liquid is subjected to continuous epoxidation reaction in a heat exchange type reactor to obtain the epoxy grease.
The continuous production method for the epoxidation of the grease is characterized in that the weight of PEG-30 is 0.005-5%, preferably 0.02-0.06% of the weight of unsaturated grease.
The continuous production method for the epoxidation of the grease is characterized in that the hydrodynamic cavitation element is a Venturi tube, a single-hole orifice plate or a multi-hole orifice plate.
The continuous production method for the epoxidation of the oil is characterized in that the unsaturated oil comprises unsaturated vegetable oil or unsaturated vegetable oil derivatives.
The continuous production method of the epoxidation of the oil and fat is characterized in that the unsaturated vegetable oil and fat comprises soybean oil; the unsaturated vegetable oil and fat derivative comprises fatty acid methyl ester or fatty acid octyl ester.
The continuous production method for the epoxidation of the grease is characterized by comprising the following specific steps:
adding PEG-30 into unsaturated grease, continuously sucking unsaturated grease containing PEG-30, formic acid and hydrogen peroxide through a grease feed port, a formic acid feed port and a hydrogen peroxide feed port respectively by a pump, conveying the mixture to a hydrodynamic cavitation element to realize oil-water two-phase mixing, allowing the mixed reaction liquid to enter a heat exchange type reactor for continuous epoxidation reaction to obtain epoxy grease, condensing the obtained epoxy grease by a condenser, and allowing the condensed epoxy grease to flow out of a product discharge port for collection;
wherein, the unsaturated grease added with PEG-30 flows into the preheater through the grease feed inlet to be preheated and then is sucked by the pump.
The continuous production method of the epoxidation of the grease is characterized in that the pressure of unsaturated grease containing PEG-30, formic acid and hydrogen peroxide conveyed by a pump and entering a hydrodynamic cavitation element is 0.5-10 atm, preferably 2-4 atm.
The continuous production method of the epoxidation of the grease is characterized in that the heat exchange type reactor is a tubular reactor or a plate type reactor.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the initial mixing of the oil phase and the water phase is enhanced by coupling the surfactant PEG-30 and the hydrodynamic cavitation technology, the hydrodynamic cavitation technology is adopted to enhance the initial mixing of the oil phase and the water phase, and the PEG-30 can greatly reduce the surface tension of the oil phase and the water phase, so that the oil phase and the water phase after initial mixing can continuously maintain the good mixing state in the subsequent reaction, even if the formed emulsion is relatively stable and micron-scale micrometric mixing of the oil phase and the water phase is realized, thus a continuous production mode can be realized; secondly, the equipment has simple structure and small occupied area, can realize large-scale industrial production, and has higher productivity and low production cost;
(2) according to the invention, only a very small amount of PEG-30 needs to be added in the process flow, so that a good mixing state of oil and water phases can be maintained, compared with the method of only adopting a hydrodynamic cavitation technology, the mixing effect is greatly enhanced, heat generated by the reaction is quickly removed through the reaction of the heat exchange type reactor, the continuous production of epoxy grease products is realized, the temperature of the reaction liquid is uniform, the product selectivity is high, the quality of the final epoxy grease product is not influenced by the addition of the PEG-30, the production cost and the process energy consumption are low, and the engineering amplification is simple.
Drawings
FIG. 1 is a process flow diagram of the present invention.
In the figure: 1, a reactor, 2 pumps, 3 pressure gauges, 4 hydrodynamic cavitation elements, 5 preheaters and 6 condensers; a grease inlet, a formic acid inlet, a hydrogen peroxide inlet, a product outlet, a cooling water inlet and a cooling water outlet.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
referring to fig. 1, 0.03% of PEG-30 by mass, 95% of formic acid by mass and 50% of hydrogen peroxide by mass are added into raw material oil (soybean oil) with an iodine value of 125, and are continuously sucked by a pump 2 through an oil feed port a, a formic acid feed port b and a hydrogen peroxide feed port c in a molar ratio of 1:1.5:0.3 (carbon-carbon double bonds in the raw material oil: hydrogen peroxide: formic acid) (wherein a preheater 5 is arranged on a pipeline between the oil feed port a and the pump 2, and a mixed solution of the raw material oil and PEG-30 is preheated to 60 ℃), and then conveyed to a hydrodynamic cavitation element 4 to realize the mixing of oil and water phases (a pressure gauge 3 is arranged on a pipeline between the pump 2 and the hydrodynamic cavitation element 4, the pressure of the reaction solution entering the hydrodynamic cavitation element 4 is controlled to be 2 bar, and the hydrodynamic cavitation element 4 is a venturi tube);
the reaction liquid mixed by the hydrodynamic cavitation element 4 enters a heat exchange type reactor 1 for epoxidation reaction at the reaction temperature of 70 ℃, the materials after 2 hours of reaction are cooled by a condenser 6, flow out of a product discharge port d and are collected, the product is separated, an oil phase product is taken, the product epoxidized soybean oil is obtained, the conversion rate of the iodine value of the product is detected to be 96%, and the selectivity of an epoxy group is detected to be 85%;
in this embodiment, the heat exchange reactor 1 is a tubular reactor, and has an outer cooling jacket, and cooling water flows in from a cooling water inlet e and flows out from a cooling water outlet f to exchange heat with the heat exchange reactor 1.
Example 2:
referring to fig. 1, 0.05% by mass of PEG-30, 95% by mass of formic acid, and 50% by mass of hydrogen peroxide were added to a raw material oil (fatty acid methyl ester) having an iodine value of 120, continuously sucking the raw material oil by a pump 2 through an oil feed inlet a, a formic acid feed inlet b and a hydrogen peroxide feed inlet c respectively according to a molar ratio of 1:1.5:0.3 (wherein a preheater 5 is arranged on a pipeline between the oil feed inlet a and the pump 2, and the raw material oil and PEG-30 mixed liquid are preheated to 60 ℃), and then conveying the raw material oil and the hydrogen peroxide to a hydrodynamic cavitation element 4 to realize mixing of oil and water phases (a pressure gauge 3 is arranged on a pipeline between the pump 2 and the hydrodynamic cavitation element 4, the pressure of the reaction liquid entering the hydrodynamic cavitation element 4 is controlled to be 3 bar, and the hydrodynamic cavitation element 4 is a single-hole orifice plate);
the reaction liquid mixed by the hydrodynamic cavitation element 4 enters a heat exchange type reactor 1 for epoxidation reaction at the reaction temperature of 70 ℃, the materials after 2 hours of reaction are cooled by a condenser 6, flow out of a product discharge port d and are collected, the product is separated, an oil phase product is taken, the epoxy fatty acid methyl ester product is obtained, the conversion rate of the iodine value of the product is detected to be 97%, and the selectivity of the epoxy group is detected to be 80%;
in this embodiment, the heat exchange reactor 1 is a tubular reactor, and has an outer cooling jacket, and cooling water flows in from a cooling water inlet e and flows out from a cooling water outlet f to exchange heat with the heat exchange reactor 1.
Example 3:
referring to fig. 1, 0.1 mass percent of PEG-30, 95 mass percent of formic acid and 50 mass percent of hydrogen peroxide are added into raw material oil (fatty acid octyl ester) with an iodine value of 90, continuously sucking the raw material oil by a pump 2 through an oil feed inlet a, a formic acid feed inlet b and a hydrogen peroxide feed inlet c respectively according to a molar ratio of 1:1.5:0.3 (wherein a preheater 5 is arranged on a pipeline between the oil feed inlet a and the pump 2, and the raw material oil and PEG-30 mixed liquid are preheated to 60 ℃), and then conveying the raw material oil and the hydrogen peroxide to a hydrodynamic cavitation element 4 to realize mixing of oil and water phases (a pressure gauge 3 is arranged on a pipeline between the pump 2 and the hydrodynamic cavitation element 4, the pressure of the reaction liquid entering the hydrodynamic cavitation element 4 is controlled to be 4 bar, and the hydrodynamic cavitation element 4 is a single-hole orifice plate);
the reaction liquid mixed by the hydrodynamic cavitation element 4 enters a heat exchange type reactor 1 for epoxidation reaction, the reaction temperature is 90 ℃, the materials after 0.5h of reaction are cooled by a condenser 6, flow out and collected through a product discharge hole d, the product is separated, an oil phase product is taken, the product epoxy fatty acid octyl ester is obtained, the iodine value conversion rate of the product is 99%, and the epoxy group selectivity is 91%;
in this embodiment, the heat exchange reactor 1 is a plate reactor, and has an outer cooling jacket, and cooling water flows in from a cooling water inlet e and flows out from a cooling water outlet f to exchange heat with the heat exchange reactor 1.
The description is given for the sole purpose of illustrating embodiments of the inventive concept and should not be taken as limiting the scope of the invention to the particular forms set forth in the embodiments, but rather as being limited only to the equivalents thereof as may be contemplated by those skilled in the art based on the teachings herein.
Claims (8)
1. A continuous production method for epoxidation of grease is characterized in that unsaturated grease and hydrogen peroxide are used as raw materials, formic acid is used as a catalyst, PEG-30 is used as an oil-water dispersing agent, a hydrodynamic cavitation element is used as a mixer, the raw materials, the catalyst and the oil-water dispersing agent are mixed by the hydrodynamic cavitation element, and the mixed reaction liquid is subjected to continuous epoxidation reaction in a heat exchange type reactor to obtain epoxy grease; the weight of the PEG-30 is 0.02-0.1% of the weight of the unsaturated oil.
2. The continuous production method of the epoxidation of the grease according to claim 1, wherein the hydrodynamic cavitation element is a venturi tube, a single-hole orifice plate or a multi-hole orifice plate.
3. The continuous production method of grease epoxidation according to claim 1, characterized in that the unsaturated grease is unsaturated vegetable grease or an unsaturated vegetable grease derivative.
4. The method for continuously producing the epoxidation of the oil according to claim 3, wherein the unsaturated vegetable oil is soybean oil; the unsaturated vegetable oil derivative is fatty acid methyl ester or fatty acid octyl ester.
5. The continuous production method for the epoxidation of grease according to claim 1, which is characterized by comprising the following steps:
adding PEG-30 into unsaturated grease, continuously sucking the unsaturated grease containing PEG-30, formic acid and hydrogen peroxide through a grease feed port (a), a formic acid feed port (b) and a hydrogen peroxide feed port (c) by a pump (2) respectively, conveying the mixture to a hydrodynamic cavitation element (4) to realize oil-water two-phase mixing, allowing the mixed reaction liquid to enter a heat exchange type reactor (1) for continuous epoxidation reaction to obtain epoxy grease, condensing the obtained epoxy grease through a condenser (6), and then flowing out of a product discharge port (d) for collection;
wherein, the unsaturated grease added with PEG-30 flows into the preheater (5) through the grease inlet (a) for preheating and then is sucked by the pump (2).
6. The continuous production method of the epoxidation of the grease, according to claim 5, characterized in that the pressure of the unsaturated grease containing PEG-30, formic acid and hydrogen peroxide delivered by the pump (2) entering the hydrodynamic cavitation element (4) is 0.5 to 10 atm.
7. The continuous production method of the epoxidation of the grease, according to claim 6, characterized in that the pressure of the unsaturated grease containing PEG-30, formic acid and hydrogen peroxide delivered by the pump (2) entering the hydrodynamic cavitation element (4) is 2-4 atm.
8. The continuous production process of epoxidation of fats and oils according to claim 5, wherein the heat exchange reactor is a tubular reactor or a plate reactor.
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| CN111333597B (en) * | 2020-04-15 | 2022-09-16 | 浙江工业大学 | Grease epoxidation continuous process |
| CN114672371B (en) * | 2022-03-17 | 2023-09-19 | 广西科技大学 | Preparation method of epoxidized oil |
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| CN108273452A (en) * | 2018-01-30 | 2018-07-13 | 浙江工业大学 | A kind of grease epoxidation reactor |
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| 不同催化体系中脂肪酸甲酯环氧化反应研究;冯树波等;《中国油脂》;20111030;第36卷(第10期);49-53 * |
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