CN107118182B - Reaction device and method for producing environment-friendly plasticizer - Google Patents
Reaction device and method for producing environment-friendly plasticizer Download PDFInfo
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- CN107118182B CN107118182B CN201710052114.4A CN201710052114A CN107118182B CN 107118182 B CN107118182 B CN 107118182B CN 201710052114 A CN201710052114 A CN 201710052114A CN 107118182 B CN107118182 B CN 107118182B
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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Abstract
The invention discloses a reaction device for producing an environment-friendly plasticizer, which comprises an esterification reaction unit, an acetylation reaction unit and an epoxidation reaction unit which are sequentially connected; the esterification reaction unit comprises an esterification material tank and an esterification micro-channel reactor which are connected in sequence; the acetylation reaction unit comprises an acetylation microchannel reactor connected with the esterification microchannel reactor, and an acetylate material tank connected between the esterification microchannel reactor and the acetylation microchannel reactor; the epoxidation reaction unit comprises an epoxidation microchannel reactor connected with the acetylation microchannel reactor, and an epoxidation material tank is connected between the acetylation microchannel reactor and the epoxidation microchannel reactor. The invention has the advantages of short reaction time and high production efficiency. The invention also provides a method for producing the environment-friendly plasticizer.
Description
Technical Field
The invention relates to the field of production of environment-friendly materials, in particular to a reaction device and a method for producing an environment-friendly plasticizer.
Background
The synthesis method of the environment-friendly plasticizer product of the epoxy vegetable oil mainly comprises the steps of esterification, acetylation, epoxidation and the like, and the production is mainly carried out by adopting an intermittent reaction kettle at present, so that the main problems are that the intermittent reaction time is long, 10-20 hours are required for each step of reaction, the side reactions are increased, and the product quality is influenced; when a mechanical stirring device is used in the reaction kettle, the heat and mass transfer efficiency is low, the excess temperature and the excess pressure are easy to occur, and the adjustment is difficult in time; the product quality is not stable, and the batches have differences and the like. Taking the last step of epoxidation as an example, a solvent-free method is adopted for sulfuric acid catalysis, namely, after the acetylated intermediate product, formic acid and concentrated sulfuric acid are added according to a certain proportion, hydrogen peroxide is added into a reaction kettle in a gradually dropping mode under continuous stirring to prevent over violent reaction. The method has long reaction time, and the reaction usually needs more than ten hours to be terminated; byproducts are easily generated, and the purity and yield of the product are influenced; and the production process is unsafe, and material flushing accidents and even explosion easily occur if the temperature is improperly controlled.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a reaction device and a method for producing an environment-friendly plasticizer, which are beneficial to shortening the reaction time and improving the production efficiency.
The invention can be realized by adopting the following technical scheme:
a reaction device for producing an environment-friendly plasticizer comprises an esterification reaction unit, an acetylation reaction unit and an epoxidation reaction unit which are connected in sequence; the esterification reaction unit comprises an esterification material tank and an esterification micro-channel reactor which are connected in sequence; the acetylation reaction unit comprises an acetylation microchannel reactor connected with the esterification microchannel reactor and a microchannel reactor connected with the esterification microchannel reactor
An acetylate material tank between the channel reactor and the acetylating microchannel reactor; the epoxidation reaction unit comprises an epoxidation microchannel reactor connected with the acetylation microchannel reactor, and an epoxidation material tank is connected between the acetylation microchannel reactor and the epoxidation microchannel reactor.
Preferably, the esterification material tank comprises a first material tank and a second material tank, and the esterification microchannel reactor comprises a first microchannel reactor and a second microchannel reactor which are used for primary esterification and are connected in series with each other, and a third microchannel reactor used for secondary esterification; the first microchannel reactor is connected with a discharge port of the first material tank; a first wiped film evaporator is connected in series between the second microchannel reactor and the third microchannel reactor, and the second material tank is connected to a branch of a communicating pipeline between the first wiped film evaporator and the third microchannel reactor; and a discharge port of the third microchannel reactor is sequentially connected with a second wiped film evaporator and a first cooler, and the first cooler is provided with a discharge port of an esterification reaction material.
Preferably, the acetylation microchannel reactor comprises a fourth microchannel reactor and a fifth microchannel reactor which are connected in series, and the acetylation material tank is a third material tank; the fourth microchannel reactor is communicated with a discharge hole of an esterification reaction material of the esterification reaction unit, and a branch of a communication pipeline between the fourth microchannel reactor and the discharge hole is provided with a third material tank; and a third wiped film evaporator is connected in series between the fourth microchannel reactor and the fifth microchannel reactor, a discharge port of the fifth microchannel reactor is sequentially connected with the fourth wiped film evaporator and a second cooler, and the second cooler is provided with a discharge port of an acetylation reaction material.
Preferably, the epoxidation microchannel reactor comprises a sixth microchannel reactor, a seventh microchannel reactor and an eighth microchannel reactor which are connected in sequence, and the epoxide material tank comprises a fourth material tank and a fifth material tank which are connected in parallel; a first temporary storage tank and a first preheater are sequentially connected in series between the acetylation reaction unit and the sixth microchannel reactor, and the first temporary storage tank is connected with a discharge port of an acetylation reaction material; the fourth material tank and the fifth material tank are both arranged on a branch of a communicating pipeline between the first preheater and the sixth microchannel reactor; and a discharge port of the eighth microchannel reactor is connected with a second temporary storage tank, and the second temporary storage tank is provided with a discharge port of an epoxidation reaction material.
Preferably, the first material tank, the first microchannel reactor, the second microchannel reactor, the third microchannel reactor and the second material tank are externally connected with circulating heat conduction oil; the fourth micro-channel reactor and the fifth micro-channel reactor are externally connected with steam; circulating water is externally connected with the first cooler, the second cooler, the sixth micro-channel reactor and the seventh micro-channel reactor; and the eighth microchannel reactor is externally connected with circulating chilled water.
Preferably, the reaction device for producing the environment-friendly plasticizer further comprises a post-treatment unit; the post-treatment unit comprises a water washing and alkali washing unit, a dehydration and deacidification unit and a decoloration and deodorization unit which are sequentially connected.
Preferably, the water washing and alkali washing unit comprises a second preheater externally connected with steam, a first separator and a second separator which are connected in sequence; a first hot water tank and a first alkali water tank are respectively connected between the second preheater and the first separator;
a second hot water tank and a second alkali water tank are respectively connected between the first separator and the second separator; the second preheater is connected with the second temporary storage tank;
the dehydration deacidification unit comprises a first drying tower, a first deacidification tower, a second deacidification tower and a second drying tower which are connected in sequence, and the first drying tower is connected with a second separator; and preheaters externally connected with steam are arranged between two adjacent devices of the second separator, the first drying tower, the first deacidification tower, the second deacidification tower and the second drying tower which are sequentially connected.
Preferably, the decolorizing and deodorizing unit comprises an activated carbon adsorption unit and a molecular distillation and deodorization unit; the activated carbon adsorption unit comprises one or more sequentially connected reaction kettles which are externally connected with steam and internally provided with activated carbon adsorbents, and the reaction kettles are connected with the second drying tower; the molecular distillation deodorization unit comprises a film processing system and a molecular distillation system which are connected in sequence; the film processing system comprises a third temporary storage tank, a third preheater, a film evaporator and a first heavy component receiving tank which are connected in sequence; the third temporary storage tank is connected with the filter, the first heavy component receiving tank is communicated with the lower part of the thin film evaporator, the upper part of the thin film evaporator is communicated with the upper part of a first condenser, and the lower part of the first condenser is communicated with a first light component receiving tank; the molecular distillation system comprises a reheater, a molecular distiller and a second heavy component receiving tank which are connected in sequence; the reheater is communicated with the first heavy component receiving tank, the lower part of the molecular distiller is also respectively communicated with a second light component receiving tank and a second condenser, and the second condenser is sequentially communicated with a cold trap, a buffer tank and a high vacuum unit; the lower parts of the second condenser and the cold trap are both communicated with a second light component receiving tank; the upper parts of the second light component-receiving tank and the second heavy component-receiving tank are communicated with each other.
The method for producing the environment-friendly plasticizer by adopting the reaction device for producing the environment-friendly plasticizer comprises the following steps:
(1) esterification reaction: adding esterification raw materials, namely vegetable oleic acid, polyhydric alcohol and an esterification catalyst, into a first material tank, heating and stirring, mixing and preheating to 130-170 ℃, and uniformly mixing the three materials; the mixed materials are pumped into a first microchannel reactor through a metering pump for reaction, the temperature of the first microchannel reactor is 160-180 ℃, and the retention time is 50-300 s; then, pumping the reaction materials into a second microchannel reactor for reaction, wherein the temperature of the second microchannel reactor is 180-200 ℃, the retention time is 50-300 s, completing a primary esterification reaction, and dehydrating the reaction product through a first wiped film evaporator; adding dibasic acid and an esterification catalyst into a second material tank, heating and stirring, mixing and preheating to 160-180 ℃, uniformly mixing the two materials, pumping the mixed material and a product dehydrated by primary esterification reaction into a third microchannel reactor by a metering pump, wherein the temperature of the third microchannel reactor is 180-200 ℃, the retention time is 80-200 s, finishing secondary esterification reaction, dehydrating the reaction product by a second wiped film evaporator, and then cooling to 110-120 ℃ in a first cooler;
(2) acetylation reaction: adding an acetylation reagent and an acetylation catalyst into a third material tank, uniformly mixing, pumping the mixture and the product obtained in the step (1) into a fourth microchannel reactor through a metering pump, performing primary acetylation reaction at the temperature of 75-85 ℃ for 50-150 s, and dehydrating through a third wiped film evaporator; then, the mixture enters a fifth microchannel reactor, the temperature of the fifth microchannel reactor is 85-95 ℃, the retention time is 80-170 s, and acetylation reaction is completed; dehydrating the reaction product through a fourth wiped film evaporator, and then cooling the reaction product to 40-50 ℃ in a second cooler;
(3) epoxidation reaction: pumping the product obtained in the step (2) into a first temporary storage tank, wherein a fourth material tank is a formic acid or acetic acid tank, a fifth material tank is a mixing tank of hydrogen peroxide and concentrated sulfuric acid or a mixing tank of hydrogen peroxide and phosphoric acid, and pumping the materials of the first temporary storage tank, the fourth material tank and the fifth material tank into a sixth microchannel reactor sequentially through a metering pump, wherein the temperature of the sixth microchannel reactor is 55-65 ℃, and the retention time is 100-250 s; then the mixture enters a seventh micro-channel reactor, wherein the temperature of the seventh micro-channel reactor is 65-75 ℃, and the retention time is 100-250 s; then quenching the mixture in an eighth microchannel reactor, wherein the temperature of the eighth microchannel reactor is 25-35 ℃, and finishing the reaction; then the crude product enters a second temporary storage tank for static layering, the upper layer of acid water is removed from a sewage treatment tank, and the lower layer of crude product waits for entering a post-treatment unit;
(4) water washing and alkali washing: testing the acid value of the lower-layer crude product obtained in the step (3), and pumping the lower-layer crude product into a first separator for washing if the acid value is qualified; if the acid value is not qualified, performing alkali washing in a first separator, and then performing water washing in a second separator; the alkali washing and water washing temperatures are all set to be 70 ℃; and (3) dewatering and deacidifying: feeding the washed crude product into a first drying tower, and vacuumizing to remove water at the temperature of 100-120 ℃; then, the crude product enters a first deacidification tower and a second deacidification tower in sequence to remove acidic substances in the crude product, wherein the temperature of the first deacidification tower is 110-120 ℃, and the temperature of the second deacidification tower is 120-130 ℃; then, the mixture enters a second drying tower, and the temperature is 130-150 ℃; decoloring and deodorizing: then, feeding the crude product into a reaction kettle of an activated carbon adsorption unit, mixing and stirring activated carbon and activated clay in the reaction kettle of the crude product for 1-2 hours at 80-90 ℃, decoloring, and then feeding the mixture into a filter for solid-liquid separation; and then, sequentially feeding the decolored crude product into a film treatment system and a molecular distillation system of a molecular distillation deodorization unit for deodorization treatment, and finally obtaining an environment-friendly plasticizer product.
Compared with the prior art, the invention has the beneficial effects that: the environment-friendly plasticizer product produced by the microchannel reaction device and the method can meet the same index requirement as the plasticizer product produced in the batch type reaction kettle, but the reaction time of each step is only a few minutes, so that the production time is greatly shortened, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of the structure of an esterification reaction unit of the present invention;
FIG. 2 is a schematic structural diagram of an acetylation reaction unit;
FIG. 3 is a schematic diagram of the structure of an epoxidation reaction unit;
FIG. 4 is a schematic diagram of the structure of a water scrubbing alkaline unit;
FIG. 5 is a schematic diagram of a dehydration deacidification unit;
FIG. 6 is a schematic view of the structure of an activated carbon adsorption unit;
FIG. 7 is a schematic diagram of a thin film processing system;
FIG. 8 is a schematic diagram of the structure of a molecular distillation system.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
As shown in fig. 1-8, a reaction apparatus for producing an environmentally friendly plasticizer includes an esterification reaction unit 1, an acetylation reaction unit 2, and an epoxidation reaction unit 3, which are connected in sequence; the esterification reaction unit 1, the acetylation reaction unit 2 and the epoxidation reaction unit 3 respectively comprise a material tank and a microchannel reactor which are connected.
Microchannel reactors, also known as micro-scale or micro-structured reactors, have characteristic dimensions of tens to hundreds of microns, much smaller than those of conventional reactors, but for reactions at the molecular level, the dimensions are still very large and therefore do not alter the chemical reaction mechanism and the intrinsic kinetic properties. The microchannel reactor enhances the chemical process by changing the heat transfer, mass transfer and flow characteristics of fluid, and has the advantages of accurate control of temperature and reaction time, safe structure, no amplification effect, stable product quality and the like.
In this embodiment, the microchannel reactors are all reinforced hybrid channel structures, which can be core-type structures, spherical baffled structures or drop-shaped structures, and the diameter of the channel is 0.25-5 mm. The esterification reaction unit 1 comprises a first material tank 11, a first microchannel reactor 12 and a second microchannel reactor 13 for primary esterification reaction, a first wiped film evaporator 14, a third microchannel reactor 15 for secondary esterification reaction, a second wiped film evaporator 16 and a first cooler 17 which are connected in sequence; a second material tank 18 is connected between the first wiped film evaporator 14 and the third microchannel reactor 15. The first material tank 11, the first micro-channel reactor 12, the second micro-channel reactor 13, the third micro-channel reactor 15 and the second material tank 18 are externally connected with circulating heat conducting oil. Stirring devices are arranged in the first material tank 11 and the second material tank 18, and a metering pump, a pressure gauge and a thermometer are arranged between the first material tank 11 and the first microchannel reactor 12 and used for conveying materials and monitoring the pressure and the temperature of the materials; thermometers are arranged at the material inlet and the material outlet of the second microchannel reactor 13 and used for monitoring the temperature of the materials.
Metering pumps and pressure gauges are arranged between the first wiped film evaporator 14 and the third microchannel reactor 15, and between the second material tank 18 and the third microchannel reactor 15, and are used for conveying materials and monitoring the pressure of the materials; after the two streams are mixed, a thermometer is placed adjacent to the third microchannel reactor 15 to monitor the temperature of the mixed stream. The first cooler 17 cools down by circulating water.
The primary esterification reaction can be an ester exchange reaction or an esterification reaction, the secondary esterification reaction can be an esterification reaction or an ester exchange reaction, the first microchannel reactor 12 and the second microchannel reactor 13 which are connected with each other are arranged in the primary esterification reaction, the temperature of different stages can be set according to requirements, and the reaction degree is improved. The ester exchange reaction and the esterification reaction are reversible reactions, and in the process of the ester exchange reaction, the esterification reaction may be accompanied by generation of moisture, which affects the progress of the reaction, so a first wiped film evaporator 14 needs to be set up to remove the moisture generated by the esterification reaction, thereby avoiding affecting the esterification reaction of a following third microchannel reactor 15, and a second wiped film evaporator 16 is set up after the third microchannel reactor 15 to remove the generated moisture, thereby avoiding affecting the subsequent acetylation reaction, and in the process of the acetylation reaction, because the moisture is removed, further esterification reaction can be promoted.
The acetylation reaction unit 2 comprises a fourth microchannel reactor 22, a third wiped film evaporator 23, a fifth microchannel reactor 24, a fourth wiped film evaporator 25 and a second cooler 26 which are connected in sequence; the fourth microchannel reactor 22 is connected to the first cooler 17, and a third material tank 21 is connected between the first cooler 17 and the fourth microchannel reactor 22. The fourth microchannel reactor 22 and the fifth microchannel reactor 24 are externally connected with steam, and the second cooler 26 is externally connected with circulating water. The acetylation reaction generates water to affect the reaction process, so dehydration is required. The twice esterified material cooled to a certain temperature by the first cooler 17 is mixed with the material from the third material tank 21, and then enters the fourth microchannel reactor 22 for preliminary acetylation reaction, and then is dehydrated by the third wiped film evaporator 23, and then enters the fifth microchannel reactor 24 through the metering pump for further acetylation reaction, and after the reaction is finished, the material is dehydrated by the fourth wiped film evaporator 25 and then enters the second cooler 26.
Two thermometers are arranged between the first cooler 17 and the fourth microchannel reactor 22, the thermometer close to the first cooler 17 is used for monitoring the temperature of the material cooled by the first cooler 17 after the esterification reaction, and the thermometer close to the fourth microchannel reactor 22 is used for monitoring the temperature of the mixed two materials. If the temperature of the two mixed materials is lower than the temperature required by the acetylation reaction, the flow of the circulating water in the first cooler 17 is reduced, the temperature of the materials after the esterification reaction is increased, and the temperature of the two mixed materials is increased. The advantage of design like this lies in relying on the temperature of material itself after the esterification to adjust the temperature of two strands of materials after mixing, does not need the additional heat exchanger to reach the purpose that reduces the energy consumption.
And a metering pump and a pressure gauge are arranged between the third material tank 21 and the fourth microchannel reactor 22, between the third wiped film evaporator 23 and the fifth microchannel reactor 24, and between the fourth wiped film evaporator 25 and the second cooler 26, and are used for conveying materials and monitoring the pressure of the materials. Thermometers are provided at the material outlets of the fourth microchannel reactor 22, the fifth microchannel reactor 24, and the second cooler 26 to monitor the temperature of the material.
The epoxidation reaction unit 3 comprises a first temporary storage tank 31, a first preheater 32, a sixth microchannel reactor 33, a seventh microchannel reactor 34, an eighth microchannel reactor 35 and a second temporary storage tank 36 which are connected in sequence; a fourth material tank 37 and a fifth material tank 38 which are connected in parallel are connected between the first preheater 32 and the sixth microchannel reactor 33; the second cooler 26 is connected to a first temporary storage tank 31. Because the epoxidation reaction belongs to a strong exothermic reaction, the sixth microchannel reactor 33 and the seventh microchannel reactor 34 both adopt external circulating water for temperature control. The eighth microchannel reactor 35 is externally connected with circulating chilled water, the temperature of the materials is rapidly reduced to about 30 ℃ by using the chilled water, quenching is carried out, and the reaction is stopped. The first preheater 32 is externally connected with steam.
After the acetylation reaction is finished, the material is cooled by the second cooler 26 and then enters the first temporary storage tank 31, after being slightly preheated by the first preheater 32, the material and two materials from the fourth material tank 37 and the fifth material tank 38 enter the sixth micro-channel reactor 33 and the seventh micro-channel reactor 34 together for epoxidation reaction, then the material enters the eighth micro-channel reactor 35 for quenching, after the epoxidation reaction is finished, the material enters the second temporary storage tank 36 for standing and layering, an upper acid water removal water treatment pool is formed, and a lower crude product waits for post-treatment.
And a metering pump and a pressure gauge are arranged between the first temporary storage tank 31 and the sixth microchannel reactor 33, between the fourth material tank 37 and the sixth microchannel reactor 33, and between the fifth material tank 38 and the sixth microchannel reactor 33, and are used for conveying materials and monitoring the pressure of the materials. Thermometers are arranged at material outlets of the first preheater 32, the sixth microchannel reactor 33, the seventh microchannel reactor 34 and the eighth microchannel reactor 35 and used for monitoring the temperature of the materials.
The wiped film evaporators are falling film evaporators.
A reaction device for producing an environment-friendly plasticizer also comprises a post-treatment unit; the post-treatment unit comprises a water washing and alkali washing unit 4, a dehydration and deacidification unit 5 and a decoloration and deodorization unit which are connected in sequence.
The water washing and alkali washing unit 4 comprises a second preheater 41 externally connected with steam, a first separator 44 and a second separator 47 which are connected in sequence; a first hot water tank 42 and a first alkali water tank 43 are respectively connected between the second preheater 41 and the first separator 44; a second hot water tank 45 and a second alkaline water tank 46 are respectively connected between the first separator 44 and the second separator 47; the second preheater 41 is connected to the second temporary storage tank 36. A metering pump and a pressure gauge are provided between the second holding tank 36 and the second preheater 41 for feeding the material and monitoring the material pressure.
The dehydration deacidification unit 5 comprises a first drying tower 51, a first deacidification tower 52, a second deacidification tower 53 and a second drying tower 54 which are connected in sequence, wherein the first drying tower 51 is connected with a second separator 47; two adjacent devices of the second separator 47, the first drying tower 51, the first deacidification tower 52, the second deacidification tower 53 and the second drying tower 54 which are connected in sequence are provided with preheaters externally connected with steam. And a metering pump and a pressure gauge are arranged between every two towers and used for conveying materials and monitoring the pressure of the materials. The four towers differ in that the first drying tower 51 is provided with only a vacuum device for removing most of the water in the crude product after washing with water in the separator; a steam introducing device is additionally arranged in the first deacidification tower 52 and the second deacidification tower 53, and residual acidic substances in the crude product are removed through the gas stripping action, so that the aim of further reducing the acid value is fulfilled; the second drying tower 54 is provided with not only a vacuum device and a steam device, but also a nitrogen device for removing residual moisture in the crude product and some low molecular substances which cannot be removed in the first deacidification tower 52 and the second deacidification tower 53.
The decolorizing and deodorizing unit comprises an activated carbon adsorption unit 6 and a molecular distillation and deodorization unit.
The activated carbon adsorption unit 6 includes one or more sequentially connected reaction kettles externally connected with steam and internally provided with activated carbon adsorbents, which are connected with the filter 62, and the reaction kettles are connected with the second drying tower 54. In this embodiment, two reaction vessels are provided. The two reaction kettles (61,63) have the same structure, and are internally provided with a steam heating device, a mechanical stirring device, a vacuum device and a nitrogen introducing device. Mixing and stirring the dehydrated and deacidified crude product with activated carbon and activated clay in a reaction kettle at the temperature of 80-90 ℃ for 1-2 h, removing colored groups in the crude product through the adsorption of the activated carbon and the activated clay to achieve the aim of decoloring, then carrying out solid-liquid separation through a filter 62, and feeding the obtained crude product into a final-step post-treatment molecular distillation deodorization unit.
The molecular distillation deodorization unit comprises a film processing system 7 and a molecular distillation system 8 which are connected in sequence.
The thin film treatment system 7 comprises a third temporary storage tank 71, a third preheater 72, a thin film evaporator 73 and a first heavy component receiving tank 74 which are connected in sequence; the third temporary storage tank 71 is connected with the filter 62, the first heavy component receiving tank 74 is communicated with the lower part of the thin film evaporator 73, the upper part of the thin film evaporator 73 is communicated with the upper part of the first condenser 75, and the lower part of the first condenser 75 is communicated with the first light component receiving tank 76. The first light component receiving tank 76, the first heavy component receiving tank 74 and the buffer tank are sequentially communicated, and the air pressure is adjusted by a common vacuum machine connected to the buffer tank; an electric flow control valve is arranged at the bottom of the first light component receiving tank 76; the upper end and the lower end of the first condenser 75 are respectively communicated with a circulating water inlet pipe and a circulating water outlet pipe. Flow control system between thin film processing system 7 and third jar 71 of keeping in sets up on the oil pipe between third preheater 72 and third jar 71 of keeping in, and it includes the valves, electric flow control valve, flow controller and rotameter, be equipped with the valves between electric flow control valve and the third jar 71 of keeping in, set up rotameter between electric flow control valve and the third preheater 72, be connected with flow controller between rotameter and the electric flow control valve, rotameter's both ends are parallelly connected with a valve behind the series connection valve respectively again. The preheating temperature control system on the film processing system is characterized in that heat conducting oil from a heat conducting oil inlet pipe is respectively pumped into the third preheater 72 and the film evaporator 73 through the four-way valve under the control of the temperature controller, the flow rate of the heat conducting oil is regulated through the valve, and the heat conducting oil discharged from the third preheater 72 and the film evaporator 73 enters a heat conducting oil outlet pipe through the four-way valve.
The molecular distillation system 8 comprises a reheater 81, a molecular distiller 82 and a second heavy component receiving tank 83 which are connected in sequence; the reheater 81 is communicated with the first heavy component receiving tank 74, the lower part of the molecular still 82 is also respectively communicated with a second light component receiving tank 84 and a second condenser 85, and the second condenser 85 is sequentially communicated with a cold trap 86, a buffer tank and a high vacuum unit; the lower portions of the second condenser 85 and the cold trap 86 are both communicated with the second light component-receiving tank 84; the upper portions of the second light component-receiving tank 84 and the second heavy component-receiving tank 83 are communicated with each other. An oil pipe at the lower end of the reheater 81 and communicated with the first heavy component receiving tank 74 is provided with a flow control system, the upper end of the reheater 81 is communicated with the upper part of the molecular distiller 82, the second condenser 85 is in liquid communication with the cold trap 86, and the cold trap 86, the buffer tank and the high vacuum unit are sequentially communicated; the upper part of the second light component receiving tank 84 is communicated with the upper part of the second heavy component receiving tank 83, and the upper part and the bottom of the second light component receiving tank 84 are provided with electric flow control valves; the lower part of the molecular distiller 82 is communicated with a circulating water inlet pipe and a circulating water outlet pipe; the upper end and the lower end of the second condenser 85 are respectively communicated with a circulating water inlet pipe and a circulating water outlet pipe; the top of the cold trap 86 is in communication with the chilled water inlet pipe and the chilled water outlet pipe. The flow control system between the reheater 81 and the first heavies receiving tank 74 and the preheat temperature control system on the molecular distillation system 8 function in a manner similar to that described above for the membrane processing system 7.
In the present embodiment, the molecular distillation system 8 is provided with two groups connected to each other. Firstly, the crude product after being adsorbed and decolored by active carbon is degassed and dehydrated by a thin film evaporation technology, and then fatty acid and low molecular alcohol are removed by two-stage molecular distillation, and finally, a decolored and deodorized environment-friendly plasticizer product A with high quality is obtained.
The method for producing the environment-friendly plasticizer comprises an esterification reaction, an acetylation reaction and an epoxidation reaction.
In the esterification reaction, the vegetable oil can be one or more of soybean oil, linseed oil, palm oil and castor oil; the polyhydric alcohol can be one or more of 1, 4-butanediol, glycerol, pentaerythritol and trimethylolpropane; the ester exchange catalyst can be one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide and calcium oxide, and the esterification catalyst can be one or more of tetrabutyl titanate, phosphoric acid and sodium phosphate; the dibasic acid may be one or more of adipic acid, phthalic anhydride, maleic anhydride, and terephthalic acid.
In the acetylation reaction, the acetylation reagent can be acetyl chloride, glacial acetic acid and acetic anhydride; the catalyst is one or more of concentrated sulfuric acid, p-toluenesulfonic acid and acidic ion exchange resin.
In the epoxidation reaction, the catalyst may be sulfuric acid or phosphoric acid.
The environment-friendly plasticizer of the binary acid bis-monoacetyl epoxy vegetable oil ester is prepared by the following steps according to the microchannel reaction device and the method:
(1) esterification reaction: adding 750g of soybean oil, 150g of glycerol and 0.25g of sodium hydroxide catalyst into a first material tank, heating and stirring, mixing and preheating to 170 ℃, and uniformly mixing the three materials; the mixed materials are pumped into a first microchannel reactor for reaction through a metering pump, the temperature of the first microchannel reactor is 170 ℃, and the retention time is 150 s; then, pumping the reaction materials into a second microchannel reactor for reaction, wherein the temperature of the second microchannel reactor is 200 ℃, the retention time is 150s, completing a primary esterification reaction which is an ester exchange reaction to form soybean oil monoester, and dehydrating the reaction product through a first wiped film evaporator; adding 12.5g of adipic acid and 0.6g of phosphoric acid catalyst into a second material tank, heating and stirring, mixing and preheating to 180 ℃, uniformly mixing the two materials, pumping the mixed material and a product obtained after the primary esterification reaction dehydration into a third microchannel reactor by a metering pump, wherein the temperature of the third microchannel reactor is 200 ℃, the retention time is 150s, finishing the secondary esterification reaction which is the esterification reaction to form binary acid bi-vegetable oil ester, dehydrating the reaction product by a second wiped film evaporator, and then cooling to 120 ℃ in a first cooler;
(2) acetylation reaction: adding 122g of acetylation reagent glacial acetic acid and 1.2g of acetylation catalyst p-toluenesulfonic acid into a third material tank, uniformly mixing, pumping the mixture and the product obtained in the step (1) into a fourth microchannel reactor through a metering pump, performing primary acetylation reaction at the temperature of 80 ℃ for 100s, and dehydrating through a third wiped film evaporator; then the mixture enters a fifth microchannel reactor, the temperature of the fifth microchannel reactor is 90 ℃, the retention time is 100s, and the acetylation reaction is completed; dehydrating the reaction product through a fourth wiped film evaporator, and then cooling the reaction product to 50 ℃ in a second cooler;
(3) epoxidation reaction: pumping the product obtained in the step (2) into a first temporary storage tank, wherein the fourth material tank is a formic acid tank, the fifth material tank is a mixing tank of hydrogen peroxide and phosphoric acid, and pumping the materials of the first temporary storage tank, the fourth material tank and the fifth material tank into a sixth microchannel reactor in sequence through a metering pump, wherein 16g of formic acid, 0.6g of phosphoric acid and 150g of hydrogen peroxide are pumped into the sixth microchannel reactor at the temperature of 60 ℃ and the retention time of 150 s; then the mixture enters a seventh microchannel reactor, the temperature of the seventh microchannel reactor is 70 ℃, and the retention time is 150 s; then quenching the mixture in an eighth microchannel reactor, wherein the temperature of the eighth microchannel reactor is 30 ℃, and finishing the reaction; then the crude product enters a second temporary storage tank for static layering, the upper layer of acid water is removed from a sewage treatment tank, and the lower layer of crude product waits for entering a post-treatment unit;
(4) water washing and alkali washing: testing the acid value of the lower-layer crude product obtained in the step (3), and pumping the lower-layer crude product into a first separator for washing if the acid value is qualified; if the acid value is not qualified, performing alkali washing in a first separator, and then performing water washing in a second separator; the alkali washing and water washing temperatures are all set to be 70 ℃; and (3) dewatering and deacidifying: feeding the washed crude product into a first drying tower, and vacuumizing to remove moisture at the temperature of 110 ℃; then, the crude product enters a first deacidification tower and a second deacidification tower in sequence to remove acidic substances in the crude product, wherein the temperature of the first deacidification tower is 120 ℃, and the temperature of the second deacidification tower is 130 ℃; then entering a second drying tower at the temperature of 140 ℃; decoloring and deodorizing: then, the crude product enters a reaction kettle of an activated carbon adsorption unit, the crude product, activated carbon and activated clay in the reaction kettle are mixed and stirred for 1.5 hours at the temperature of 85 ℃, decolorization is carried out, and then the crude product enters a filter for solid-liquid separation; and then, sequentially feeding the decolored crude product into a film treatment system and a molecular distillation system of a molecular distillation deodorization unit for deodorization treatment, and finally obtaining an environment-friendly plasticizer product.
The diacid bis-acetyl epoxy vegetable oil ester environment-friendly plasticizer is prepared according to the method of an intermittent reaction kettle of Chinese patent CN105085442 at the same time, the reaction time is 24 hours, the crude product is processed by a post-processing unit of the invention, and the following nodes are respectively tested:
intermediate product 1: a product after primary esterification reaction;
intermediate product 2: a product after secondary esterification reaction;
intermediate product 3: and (4) acetylation reacting to obtain the product.
Index pair ratio table 1:
TABLE 1
Meanwhile, the product indexes obtained after respectively performing post-treatment on the products obtained in the microchannel reaction device and the batch reactor are shown in Table 2:
TABLE 2
The environment-friendly plasticizer product obtained by the microchannel reaction device can meet the index requirement same as that of the batch reaction kettle, but the reaction time of each step is only a few minutes, and the reaction time of the batch reaction kettle is 4-10 hours, so that the reaction time of the microchannel reaction device is far shorter than that of the batch reaction kettle, and the production efficiency is greatly improved.
In the actual production, the proportion, the temperature and the time of the used raw materials can be adjusted according to the requirements.
The present invention has been described in connection with the preferred embodiments, but the present invention is not limited to the embodiments disclosed above, and is intended to cover various modifications, equivalent combinations, which are within the spirit of the invention.
Claims (9)
1. A reaction device for producing an environment-friendly plasticizer is characterized by comprising an esterification reaction unit, an acetylation reaction unit and an epoxidation reaction unit which are sequentially connected; the esterification reaction unit comprises an esterification material tank and an esterification micro-channel reactor which are connected in sequence; the acetylation reaction unit comprises an acetylation microchannel reactor connected with the esterification microchannel reactor, and an acetylate material tank connected between the esterification microchannel reactor and the acetylation microchannel reactor; the epoxidation reaction unit comprises an epoxidation microchannel reactor connected with the acetylation microchannel reactor, an epoxide material tank is connected between the acetylation microchannel reactor and the epoxidation microchannel reactor,
the esterification material tank comprises a first material tank and a second material tank, and the esterification micro-channel reactor comprises a first micro-channel reactor and a second micro-channel reactor which are used for primary esterification and are mutually connected in series, and a third micro-channel reactor used for secondary esterification; the first microchannel reactor is connected with a discharge port of the first material tank; a first wiped film evaporator is connected in series between the second microchannel reactor and the third microchannel reactor, and the second material tank is connected to a branch of a communicating pipeline between the first wiped film evaporator and the third microchannel reactor; and a discharge port of the third microchannel reactor is sequentially connected with a second wiped film evaporator and a first cooler, and the first cooler is provided with a discharge port of an esterification reaction material.
2. The reaction device for producing the environment-friendly plasticizer according to claim 1, wherein the acetylation microchannel reactor comprises a fourth microchannel reactor and a fifth microchannel reactor which are connected in series, and the acetylation material tank is a third material tank; the fourth microchannel reactor is communicated with a discharge hole of an esterification reaction material of the esterification reaction unit, and a branch of a communication pipeline between the fourth microchannel reactor and the discharge hole is provided with a third material tank; a third wiped film evaporator is connected in series between the fourth microchannel reactor and the fifth microchannel reactor, a discharge port of the fifth microchannel reactor is sequentially connected with the fourth wiped film evaporator and a second cooler, and the second cooler is provided with a discharge port of an acetylation reaction material;
the epoxidation microchannel reactor comprises a sixth microchannel reactor, a seventh microchannel reactor and an eighth microchannel reactor which are sequentially connected, and the epoxide material tank comprises a fourth material tank and a fifth material tank which are mutually connected in parallel; a first temporary storage tank and a first preheater are sequentially connected in series between the acetylation reaction unit and the sixth microchannel reactor, and the first temporary storage tank is connected with a discharge port of an acetylation reaction material; the fourth material tank and the fifth material tank are both arranged on a branch of a communicating pipeline between the first preheater and the sixth microchannel reactor; and a discharge port of the eighth microchannel reactor is connected with a second temporary storage tank, and the second temporary storage tank is provided with a discharge port of an epoxidation reaction material.
3. The reaction device for producing the environment-friendly plasticizer according to claim 1, wherein the acetylation microchannel reactor comprises a fourth microchannel reactor and a fifth microchannel reactor which are connected in series, and the acetylation material tank is a third material tank; the fourth microchannel reactor is communicated with a discharge hole of an esterification reaction material of the esterification reaction unit, and a branch of a communication pipeline between the fourth microchannel reactor and the discharge hole is provided with a third material tank; and a third wiped film evaporator is connected in series between the fourth microchannel reactor and the fifth microchannel reactor, a discharge port of the fifth microchannel reactor is sequentially connected with the fourth wiped film evaporator and a second cooler, and the second cooler is provided with a discharge port of an acetylation reaction material.
4. The reaction device for producing the environment-friendly plasticizer according to claim 1, wherein the epoxidation microchannel reactor comprises a sixth microchannel reactor, a seventh microchannel reactor and an eighth microchannel reactor which are connected in sequence, and the epoxide tank comprises a fourth material tank and a fifth material tank which are connected in parallel with each other; a first temporary storage tank and a first preheater are sequentially connected in series between the acetylation reaction unit and the sixth microchannel reactor, and the first temporary storage tank is connected with a discharge port of an acetylation reaction material; the fourth material tank and the fifth material tank are both arranged on a branch of a communicating pipeline between the first preheater and the sixth microchannel reactor; and a discharge port of the eighth microchannel reactor is connected with a second temporary storage tank, and the second temporary storage tank is provided with a discharge port of an epoxidation reaction material.
5. The reaction device for producing the environment-friendly plasticizer according to any one of claim 2, wherein the first material tank, the first microchannel reactor, the second microchannel reactor, the third microchannel reactor and the second material tank are externally connected with circulating heat conducting oil; the fourth micro-channel reactor and the fifth micro-channel reactor are externally connected with steam; circulating water is externally connected with the first cooler, the second cooler, the sixth micro-channel reactor and the seventh micro-channel reactor; and the eighth microchannel reactor is externally connected with circulating chilled water.
6. The reaction device for producing eco-friendly plasticizer according to claim 5, further comprising a post-treatment unit; the post-treatment unit comprises a water washing and alkali washing unit, a dehydration and deacidification unit and a decoloration and deodorization unit which are sequentially connected.
7. The reaction device for producing the environment-friendly plasticizer according to claim 6, wherein the water washing and alkali washing unit comprises a second preheater externally connected with steam, a first separator and a second separator which are connected in sequence; a first hot water tank and a first alkali water tank are respectively connected between the second preheater and the first separator; a second hot water tank and a second alkali water tank are respectively connected between the first separator and the second separator; the second preheater is connected with the second temporary storage tank;
the dehydration deacidification unit comprises a first drying tower, a first deacidification tower, a second deacidification tower and a second drying tower which are connected in sequence, and the first drying tower is connected with a second separator; and preheaters externally connected with steam are arranged between two adjacent devices of the second separator, the first drying tower, the first deacidification tower, the second deacidification tower and the second drying tower which are sequentially connected.
8. The reaction device for producing the environmentally friendly plasticizer according to claim 7, wherein the decoloring and deodorizing unit comprises an activated carbon adsorption unit and a molecular distillation and deodorization unit;
the activated carbon adsorption unit comprises one or more sequentially connected reaction kettles which are externally connected with steam and internally provided with activated carbon adsorbents, and the reaction kettles are connected with the second drying tower;
the molecular distillation deodorization unit comprises a film processing system and a molecular distillation system which are connected in sequence;
the film processing system comprises a third temporary storage tank, a third preheater, a film evaporator and a first heavy component receiving tank which are connected in sequence; the third temporary storage tank is connected with the filter, the first heavy component receiving tank is communicated with the lower part of the thin film evaporator, the upper part of the thin film evaporator is communicated with the upper part of a first condenser, and the lower part of the first condenser is communicated with a first light component receiving tank;
the molecular distillation system comprises a reheater, a molecular distiller and a second heavy component receiving tank which are connected in sequence; the reheater is communicated with the first heavy component receiving tank, the lower part of the molecular distiller is also respectively communicated with a second light component receiving tank and a second condenser, and the second condenser is sequentially communicated with a cold trap, a buffer tank and a high vacuum unit; the lower parts of the second condenser and the cold trap are both communicated with a second light component receiving tank; the upper parts of the second light component-receiving tank and the second heavy component-receiving tank are communicated with each other.
9. A method for producing an eco-friendly plasticizer using the reaction apparatus for producing an eco-friendly plasticizer according to claim 8, comprising the steps of:
(1) esterification reaction: adding esterification raw materials, namely vegetable oleic acid, polyhydric alcohol and an esterification catalyst, into a first material tank, heating and stirring, mixing and preheating to 130-170 ℃, and uniformly mixing the three materials; the mixed materials are pumped into a first microchannel reactor through a metering pump for reaction, the temperature of the first microchannel reactor is 160-180 ℃, and the retention time is 50-300 s; then, pumping the reaction materials into a second microchannel reactor for reaction, wherein the temperature of the second microchannel reactor is 180-200 ℃, the retention time is 50-300 s, completing a primary esterification reaction, and dehydrating the reaction product through a first wiped film evaporator; adding dibasic acid and an esterification catalyst into a second material tank, heating and stirring, mixing and preheating to 160-180 ℃, uniformly mixing the two materials, pumping the mixed material and a product dehydrated by primary esterification reaction into a third microchannel reactor by a metering pump, wherein the temperature of the third microchannel reactor is 180-200 ℃, the retention time is 80-200 s, finishing secondary esterification reaction, dehydrating the reaction product by a second wiped film evaporator, and then cooling to 110-120 ℃ in a first cooler;
(2) acetylation reaction: adding an acetylation reagent and an acetylation catalyst into a third material tank, uniformly mixing, pumping the mixture and the product obtained in the step (1) into a fourth microchannel reactor through a metering pump, performing primary acetylation reaction at the temperature of 75-85 ℃ for 50-150 s, and dehydrating through a third wiped film evaporator; then, the mixture enters a fifth microchannel reactor, the temperature of the fifth microchannel reactor is 85-95 ℃, the retention time is 80-170 s, and acetylation reaction is completed; dehydrating the reaction product through a fourth wiped film evaporator, and then cooling the reaction product to 40-50 ℃ in a second cooler;
(3) epoxidation reaction: pumping the product obtained in the step (2) into a first temporary storage tank, wherein a fourth material tank is a formic acid or acetic acid tank, a fifth material tank is a mixing tank of hydrogen peroxide and concentrated sulfuric acid or a mixing tank of hydrogen peroxide and phosphoric acid, and pumping the materials of the first temporary storage tank, the fourth material tank and the fifth material tank into a sixth microchannel reactor sequentially through a metering pump, wherein the temperature of the sixth microchannel reactor is 55-65 ℃, and the retention time is 100-250 s; then the mixture enters a seventh micro-channel reactor, wherein the temperature of the seventh micro-channel reactor is 65-75 ℃, and the retention time is 100-250 s; then quenching the mixture in an eighth microchannel reactor, wherein the temperature of the eighth microchannel reactor is 25-35 ℃, and finishing the reaction; then the crude product enters a second temporary storage tank for static layering, the upper layer of acid water is removed from a sewage treatment tank, and the lower layer of crude product waits for entering a post-treatment unit;
(4) water washing and alkali washing: testing the acid value of the lower-layer crude product obtained in the step (3), and pumping the lower-layer crude product into a first separator for washing if the acid value is qualified; if the acid value is not qualified, performing alkali washing in a first separator, and then performing water washing in a second separator; the alkali washing and water washing temperatures are all set to be 70 ℃;
and (3) dewatering and deacidifying: feeding the washed crude product into a first drying tower, and vacuumizing to remove water at the temperature of 100-120 ℃; then, the crude product enters a first deacidification tower and a second deacidification tower in sequence to remove acidic substances in the crude product, wherein the temperature of the first deacidification tower is 110-120 ℃, and the temperature of the second deacidification tower is 120-130 ℃; then, the mixture enters a second drying tower, and the temperature is 130-150 ℃;
decoloring and deodorizing: then, feeding the crude product into a reaction kettle of an activated carbon adsorption unit, mixing and stirring the crude product, activated carbon and activated clay in the reaction kettle for 1-2 hours at the temperature of 80-90 ℃, decoloring, and then feeding the mixture into a filter for solid-liquid separation; and then, sequentially feeding the decolored crude product into a film treatment system and a molecular distillation system of a molecular distillation deodorization unit for deodorization treatment, and finally obtaining an environment-friendly plasticizer product.
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| CN102993133A (en) * | 2013-01-08 | 2013-03-27 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester with microreactor one-step method |
| CN105085442A (en) * | 2015-07-23 | 2015-11-25 | 广州市海珥玛植物油脂有限公司 | Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof |
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| CN102993133A (en) * | 2013-01-08 | 2013-03-27 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester with microreactor one-step method |
| CN105085442A (en) * | 2015-07-23 | 2015-11-25 | 广州市海珥玛植物油脂有限公司 | Diacid bismonoacetyl epoxy vegetable oil ester and synthetic method thereof |
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