CN107857744B - Production process of epoxidized fatty acid methyl ester plasticizer and obtained plasticizer - Google Patents
Production process of epoxidized fatty acid methyl ester plasticizer and obtained plasticizer Download PDFInfo
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- CN107857744B CN107857744B CN201610840082.XA CN201610840082A CN107857744B CN 107857744 B CN107857744 B CN 107857744B CN 201610840082 A CN201610840082 A CN 201610840082A CN 107857744 B CN107857744 B CN 107857744B
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a production process of an epoxidized fatty acid methyl ester plasticizer, which comprises an epoxy step, a post-treatment step and a filter pressing step, wherein a steam stripping step is also included between the post-treatment step and the filter pressing step, the steam stripping step is subjected to feedback control by detecting the flash point of a product, and the flash point of the product is over 195; the stripping step is carried out in a stripping tower, the temperature of the stripping tower is 110-120 ℃, and the stripping pressure is 500-1500 Pa. The invention also provides the plasticizer prepared by the production process. Compared with the old process, when the raw materials with poor quality in the same batch are used, the process can improve the flash point from 188-190 ℃ to more than 195 ℃, so that the product quality is ensured and the raw material cost is reduced.
Description
Technical Field
The invention relates to the technical field of plasticizer preparation, in particular to a production process of an epoxidized fatty acid methyl ester plasticizer and an obtained plasticizer.
Background
Plasticizers, also commonly referred to as plasticizers. The plasticizer is a polymer material assistant widely used in industry, and the flexibility of the plasticizer can be enhanced by adding the plasticizer in plastic processing, the plasticizer is easy to process, and the plasticizer can be legally used for industrial application. Plasticizers are classified into aliphatic dibasic acid esters, phthalic acid esters (including phthalic acid esters and terephthalic acid esters), benzene polycarboxylic acid esters, benzoic acid esters, polyol esters, chlorinated hydrocarbons, epoxies, citric acid esters, polyesters and the like.
Epoxy plasticizers are less toxic and have been approved in many countries for use in food and pharmaceutical packaging, and are the only epoxy plasticizers approved by the U.S. drug administration for use in food packaging. The PVC heat stabilizer is an auxiliary heat stabilizer commonly used for PVC, has higher synergistic effect when being matched with the heat stabilizer, is suitable for soft PVC products, particularly soft PVC products exposed to sunlight, and is not usually used for hard PVC products.
Epoxy plasticizers are less toxic and have been approved in many countries for use in food and pharmaceutical packaging, and are the only epoxy plasticizers approved by the U.S. drug administration for use in food packaging. The PVC heat stabilizer is an auxiliary heat stabilizer commonly used for PVC, has higher synergistic effect when being matched with the heat stabilizer, is suitable for soft PVC products, particularly soft PVC products exposed to sunlight, and is not usually used for hard PVC products.
The epoxy fatty acid methyl ester is light yellow liquid at normal temperature, is a novel environment-friendly plasticizer taking the fatty acid methyl ester as a main raw material, and is a nontoxic and tasteless PVC plasticizer and stabilizer. It is widely accepted in the industry that it can not only completely or partially replace OP plasticizer to produce nontoxic and environment-friendly PVC products for food packaging, medical supplies, toys and water supply pipelines, etc., but also be used as nontoxic plasticizer and softener of cellulose resin and synthetic rubber, and in the processing of products, the addition of epoxy fatty acid methyl ester can obviously improve the physical properties of the products and prolong the aging time, and has good synergistic effect when used together with metal stabilizers such as barium, cadmium, zinc, etc. In addition, the lubricating oil also has good lubricating property, compatibility and dispersibility, and can be used as a surfactant and a dispersant to be applied to the production industries of epoxy coatings, epoxy resins and the like.
In the prior art, the production process of the epoxy fatty acid methyl ester plasticizer mainly comprises seven steps of epoxy, water washing, alkali washing, water washing, dehydration, heat preservation and filter pressing, and is mainly provided with an epoxy kettle, a post-treatment kettle and a filter press. The epoxy reaction is carried out in an epoxy kettle, and the steps of alkali washing, water washing, dehydration and heat preservation are carried out in a post-treatment kettle. Because the fat methyl ester as the raw material is mostly refined from illegal cooking oil at present or is prepared from other raw materials with complex components, the product quality is uncontrollable, and the prior art has no controllability on different raw materials.
Disclosure of Invention
The invention improves the prior art, provides the production process of the epoxidized fatty acid methyl ester plasticizer and the obtained plasticizer, realizes the adjustability of the device to light component removal, improves the adaptability to different quality raw materials, and improves the flash point of the final plasticizer product from 188-plus-material 190 ℃ to more than 195 ℃.
A production process of an epoxidized fatty acid methyl ester plasticizer comprises an epoxy step, a post-treatment step and a filter pressing step, wherein a stripping step is further included between the post-treatment step and the filter pressing step, the stripping step is subjected to feedback control by detecting the flash point of a product, and the flash point of the product is over 195 ℃.
Preferably, the stripping step is carried out in a stripping tower, the temperature of the stripping tower is 110-120 ℃, the moisture content of the materials is guaranteed, and the energy loss of water vapor is reduced. The stripping pressure is 500-1500 Pa. By selecting the scheme, the steam stripping effect is ensured, the light component removing capacity can be improved by selecting the vacuum condition, and the product quality is ensured.
Preferably, the raw material used in the epoxy step in the present invention is various fatty acid methyl ester raw materials, such as commercially available finished fatty acid methyl ester (which may be various long-chain fatty acid methyl esters or mixtures, the long-chain fatty acid methyl ester is typically C8-C18 fatty acid methyl esters, such as methyl palmitate, 16-carbon methyl ester, etc.), and other fatty acid methyl esters also include waste oils or various plant and animal fats and oils. Preferably, the fatty acid methyl ester raw material adopted in the epoxy step has an acid value of 0.1-0.5, an iodine value of 70-120, a color of 40-180 and a flash point of 120-180 ℃. Preferably, the raw material of the fatty methyl ester adopted in the epoxy step is illegal cooking oil; further solves the technical problem that the product flash point can not meet the requirement when the illegal cooking oil is adopted as the raw material in the prior art.
The invention improves the prior art, namely a stripping tower is added behind the post-treatment kettle. The raw materials are firstly epoxidized in an epoxy kettle, then enter a post-treatment kettle for water washing, alkali washing, water washing, dehydration and heat preservation, then enter a stripping tower for steam stripping, and are subjected to filter pressing after the steam stripping is finished. The process variation is primarily the addition of a stripping section after the finishing section.
Preferably, the liquid level of the tower plate of the stripping tower is below 35 cm, so that the surface area to volume ratio of the liquid is controlled, the stripping effect is controlled, and the final product result is ensured; the steam stripping pressure is 3-4 kg force/square centimeter.
In the stripping tower, the feeding amount of the original material to be stripped per hour is 2-3 tons, preferably, the feeding amount is subjected to feedback control according to the treatment amount and the flash point requirement of the product, for example, the feeding amount can be as large as possible under the condition of meeting the flash point requirement, and the reaction time is reduced; the consumption of stripping steam at the lower section of the stripping tower is 2-3 tons/hour. The saturated steam partial pressure of the light component in the gas phase is influenced by the size and the dosage of the water vapor pressure, the light component removal capacity of the stripping tower can be adjusted by adjusting the water vapor pressure and the dosage, and the quality of the final product is ensured.
Preferably, the flash point of the product is 195-198 ℃.
The invention also provides an epoxy fatty acid methyl ester plasticizer which is prepared by the production process of the epoxy fatty acid methyl ester plasticizer in any scheme.
Aiming at a product scheme, the flash point of the product is 195-198 ℃ as preferable.
The stripping tower of the invention mainly controls the light component removing capacity of the tower by adjusting the feeding amount, the steam pressure of stripping water and the using amount; the control of the operating parameters of the stripping tower is realized by detecting the flash point value of the product. After the material is stripped, the material is pumped into a filter-pressing tank by a pump at the bottom of the tower, and a finished product is obtained after filter pressing.
The production process of the invention mainly comprises the steps of epoxy, water washing, alkali washing, water washing, dehydration, heat preservation and filter pressing, and the steps of epoxy, water washing, alkali washing, water washing, dehydration, heat preservation, steam stripping and filter pressing are changed into the steps of epoxy, water washing, alkali washing, water washing, dehydration. The main production equipment is composed of an epoxy kettle, a post-treatment kettle and a filter press, wherein the epoxy kettle, the post-treatment kettle, a stripping tower and the filter press are changed into the epoxy kettle, the post-treatment kettle, the stripping tower and the filter press.
The original swill oil can be selected from various inferior oils existing in life, such as recycled swill oil, waste frying oil, food and waste grease generated by related enterprises and the like. Or an oil separation tank of a sewer of a large-scale urban restaurant. The above-mentioned drainage oil can be used as the starting material of the present invention by simple pretreatment. According to the flash point change of the product, the stripping parameters are adjusted in time, and finally the high-quality plasticizer product can be obtained.
Compared with the old process, when the raw materials with poor quality in the same batch are used, the process can improve the flash point from 188-190 ℃ to more than 195 ℃, so that the product quality is ensured and the raw material cost is reduced.
Detailed Description
The present invention is further illustrated by the following examples so that those skilled in the art can more understand the present invention:
according to the material flow direction, the device comprises an epoxy kettle, a post-treatment kettle, a stripping tower and a filter press, wherein the epoxy kettle and the post-treatment kettle can completely adopt the process conditions disclosed in the prior art, and the stripping tower is additionally arranged between the post-treatment kettle and the filter press. The stripping column comprises: (1) the raw material inlet after epoxy and post-treatment is a liquid feed inlet; (2) a water vapor inlet, namely a gas feed inlet; (3) a gas outlet; and (4) a liquid discharge port, wherein the material discharged from the liquid discharge port is the target product epoxy fatty acid methyl ester plasticizer.
Example 1
Taking 60 tons of daily handling capacity as an example, taking illegal cooking oil methyl ester of east China river energy science and technology Limited, Zhejiang as a raw material for epoxidation, wherein the acid value of the raw material is 0.15, the iodine value is 80, the color is 90#, the flash point is 169 ℃, the epoxidized material is dehydrated in a post-treatment kettle, the temperature is kept for 2 hours at 110 ℃ and 1 kilopascal, then the epoxidized material is pumped into a stripping tower by a pump, the feeding amount per hour is 2 tons, the feeding amount is adjusted according to the handling capacity and the product flash point, the surface area to volume ratio of liquid is mainly controlled so as to ensure that the liquid level of a tower plate is below 35 centimeters, the final product result is ensured, and the stripping effect is controlled. The pressure of the stripping tower is controlled to be about 1 kilopascal, the stripping effect is also ensured, and the light removal capacity can be improved by the vacuum condition. The temperature is controlled to be 110-115 ℃ by an outer wall coil pipe (the temperature of a tower plate in the tower lifter), the moisture content of the material is ensured, and the energy loss of water vapor is reduced. The steam pressure of the steam-extracting water at the lower section of the tower is 3 kg/cm2The dosage is 2 tons/hour, the saturated steam partial pressure of the light component in the gas phase is influenced by the size and dosage of the water vapor pressure, and the light component removal capacity of the stripping tower can be adjusted by adjusting the water vapor pressure and dosage. The stripping column is operated primarily by adjusting the feed and stripping steamThe light component removal capacity of the tower is controlled. After the material is stripped, the material is pumped into a filter-pressing tank by a pump at the bottom of the tower, and a finished product is obtained after filter pressing.
Example 2
Taking 60 tons of daily handling capacity as an example, using fatty acid methyl ester of Jiangsu Jiemei biological energy recovery Limited company as a raw material to perform epoxidation, wherein the acid value of the raw material is 0.35, the iodine value is 95.94, the color is 150#, the flash point is 172 ℃, the epoxidized material is dehydrated in a post-treatment kettle, the temperature is kept for 2 hours at 110 ℃ and 1 kilopascal, then the epoxidized material is pumped into a stripping tower by a pump, the feeding amount per hour is 3 tons, the feeding amount is adjusted according to the handling capacity and the product flash point, the surface area to volume ratio of liquid is mainly controlled so as to ensure that the liquid level of a tower plate is below 35 centimeters, the final product result is ensured, and the stripping effect is controlled. The pressure of the stripping tower is controlled to be about 1 kilopascal, the stripping effect is also ensured, and the light removal capacity can be improved by the vacuum condition. The temperature is controlled at 115-120 ℃ by an outer wall coil pipe (the temperature of a tower plate in the tower lifter), the moisture content of the material is ensured, and the energy loss of water vapor is reduced. The steam pressure of the steam-extracting water at the lower section of the tower is 4 kg/cm2The dosage is 3 tons/hour, the saturated steam partial pressure of the light component in the gas phase is influenced by the size and dosage of the water vapor pressure, and the light component removal capacity of the stripping tower can be adjusted by adjusting the water vapor pressure and dosage. The stripping column controls the light ends removal capacity of the column primarily by adjusting the feed and stripping steam. After the material is stripped, the material is pumped into a filter-pressing tank by a pump at the bottom of the tower, and a finished product is obtained after filter pressing.
Example 3
Taking 60 tons of daily handling capacity as an example, using refined fatty acid methyl ester of Thangshan Jinhai biodiesel GmbH as a raw material for epoxidation, wherein the acid value of the raw material is 0.22, the iodine value is 105, the color is 65#, the flash point is 175 ℃, the epoxidized material is dehydrated in a post-treatment kettle, the temperature is kept for 2 hours at 110 ℃ and 1 kilopascal, then the epoxidized material is pumped into a stripping tower by a pump, the feeding amount per hour is 2.5 tons, the feeding amount is adjusted according to the handling capacity and the product flash point requirement, mainly aiming at ensuring that the liquid level of a tower plate is below 35 centimeters, controlling the surface area to volume ratio of liquid, ensuring the final product result and further controlling the stripping effect. The pressure of the stripping tower is controlled atAbout 1 kPa, which is also to ensure the stripping effect, and the vacuum condition can improve the light-weight removal capability. The temperature is controlled at 115-120 ℃ by an outer wall coil pipe (the temperature of a tower plate in the tower lifter), the moisture content of the material is ensured, and the energy loss of water vapor is reduced. The steam pressure of stripping water at the lower section of the tower is 3.5 kg/cm2The dosage is 2.5 tons/hour, the saturated steam partial pressure of the light component in the gas phase is influenced by the size and dosage of the water vapor pressure, and the light component removal capacity of the stripping tower can be adjusted by adjusting the water vapor pressure and dosage. The stripping column controls the light ends removal capacity of the column primarily by adjusting the feed and stripping steam. After the material is stripped, the material is pumped into a filter-pressing tank by a pump at the bottom of the tower, and a finished product is obtained after filter pressing.
Meanwhile, the same conditions as in example 1 are adopted, except that the step of steam stripping is eliminated, and direct filtration is carried out after post-treatment; the product obtained was used as a control.
Effect data, the plasticizers prepared in examples 1-3 were subjected to a flash point test and the results are shown in table 1:
TABLE 1
| Sample (I) | Example 1 | Example 2 | Example 3 | Comparative sample |
| Flash point/. degree.C | 195～197 | 196～198 | 195～197 | 188-190 |
As can be seen from the results in Table 1, when the same batch of raw materials with poor quality are used, the flash point of the new process can be increased from 188-190 ℃ to over 195 ℃, so that the product quality is ensured and the raw material cost is reduced. A plasticizer having stable properties can be obtained from a waste oil raw material having a complicated composition.
Claims (1)
1. A production process of an epoxidized fatty acid methyl ester plasticizer comprises an epoxy step, a post-treatment step and a filter pressing step, and is characterized in that a steam stripping step is further included between the post-treatment step and the filter pressing step, and the steam stripping step is subjected to feedback control by detecting the flash point of a product; the stripping step is carried out in a stripping tower, the temperature of the stripping tower is 110-120 ℃, and the stripping pressure is 500-1500 Pa; the liquid level of a tower plate of the stripping tower is below 35 cm, and the steam stripping pressure is 3-4 kilogram force/square cm; in a stripping tower, the feeding amount of an original material to be stripped per hour is 2-3 tons, and the steam stripping steam consumption at the lower section of the tower is 2-3 tons/hour; the acid value of the fatty acid methyl ester raw material adopted in the epoxy step is 0.1-0.5, the iodine value is 70-120, and the flash point is 120-180 ℃; the flash point of the product is 195-198 ℃.
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| CN114920716B (en) * | 2022-04-29 | 2024-04-02 | 浙江嘉澳环保科技股份有限公司 | Continuous production process and system of methyl epoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104592169A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Method for preparing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material |
| CN105175362A (en) * | 2015-07-14 | 2015-12-23 | 浙江嘉澳环保科技股份有限公司 | High-compatibility modified epoxy plasticizer preparation method and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104592169A (en) * | 2015-01-21 | 2015-05-06 | 吴俊荣 | Method for preparing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material |
| CN105175362A (en) * | 2015-07-14 | 2015-12-23 | 浙江嘉澳环保科技股份有限公司 | High-compatibility modified epoxy plasticizer preparation method and product thereof |
Non-Patent Citations (1)
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| 地沟油改性制备PVC用环氧脂肪酸甲酯增塑剂;贾茂林等;《中国塑料》;20141130;第28卷(第11期);第82-87页 * |
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