CN111517950A - Preparation method of phthalate plasticizer - Google Patents
Preparation method of phthalate plasticizer Download PDFInfo
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- CN111517950A CN111517950A CN202010400128.2A CN202010400128A CN111517950A CN 111517950 A CN111517950 A CN 111517950A CN 202010400128 A CN202010400128 A CN 202010400128A CN 111517950 A CN111517950 A CN 111517950A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention provides a preparation method of phthalate plasticizer, which comprises the steps of esterification, crude dealcoholization, cooling and deacidification agent addition, dealcoholization and filtration, and the preparation method does not need decolorant treatment, the chromaticity of the prepared phthalate plasticizer product can reach 10-15# by platinum-cobalt standard color comparison, phthalic anhydride and sec-octanol are used as raw materials, the acid value of the di-sec-octyl phthalate prepared by the preparation method is less than or equal to 0.05mgKOH/g, the water content is less than or equal to 0.05%, the content is more than or equal to 99.5%, the alcohol content is less than or equal to 0.005%, and meanwhile, the neutralization and water washing steps can be reduced, the wastewater amount is reduced, the alkali washing, water washing and settling time is saved, the production cost is greatly reduced, and the production benefit is increased.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of a phthalate plasticizer.
Background
The plasticizer is widely applied to the field of plastic product processing, and with the rapid development of the plastic industry, higher requirements are put forward on the quality of the plasticizer, particularly the color control aspect of the plasticizer product is severe, and the color of the plasticizer product is closely related to the light transmittance and the refractive index of downstream products. At present, the preparation process of the plasticizer is mainly decolored by using a decolorant, and the activated carbon is used as the most extensive decolorant, has low price, mature application technology and better decoloration effect, and is applied to the fields of plasticizer decoloration and other decoloration adsorption.
However, the use amount of the activated carbon is large in the use process, the activated carbon can adsorb a large part of plasticizer materials, a large amount of materials are wasted, the adsorption capacity of the activated carbon is limited, and colored substances cannot be completely adsorbed. Although the activated carbon has more advantages as a decoloring agent, the activated carbon also has a plurality of defects, and the research on a production process capable of effectively removing the color of a plasticizer product has positive significance.
CN201510846882.8 discloses a dibutyl phthalate plasticizer production process, which comprises the steps of carrying out esterification reaction on phthalic anhydride, n-butyl alcohol and a solid acid catalyst, filtering out the solid catalyst after the reaction is finished, and carrying out neutralization, water washing, steam stripping and fine filtration to obtain a dibutyl phthalate plasticizer product, wherein diatomite and active carbon are added into the refined ester for decolorization, 4-6 kg of solid waste is generated in each ton of the product, and the dibutyl phthalate plasticizer product is difficult to recycle and high in treatment cost.
CN200610085456.8 discloses a phthalate esterification production process, which comprises the steps of preparing monoester by taking phthalic anhydride and corresponding excessive alcohols as raw materials, adding aluminum oxide solid and sodium hydroxide aqueous solution, heating to generate sodium aluminate, adding lithium hydroxide into the sodium aluminate to catalyze diester reaction, thus improving the quality of dioctyl phthalate finished products, and the color of the prepared products is within 10-20 APHA.
CN200510017105.9 discloses a method for producing diisodecyl phthalate, which comprises using phthalic anhydride and isodecyl alcohol as raw materials, using isopropyl titanate as a catalyst, carrying out esterification, dealcoholization, alkali wash and water wash, and stripping to obtain diisodecyl phthalate, wherein the chroma of the obtained diisodecyl phthalate is 30-15 # by platinum-cobalt standard color comparison, and the ester content is 99.8-99.9%.
Disclosure of Invention
In order to solve the problems in the prior art and further optimize the prior art, the invention provides a preparation method of phthalate plasticizer, which aims to realize the following purposes:
(1) the product transparency is improved, and the chroma is reduced;
(2) the acid value of the product is reduced;
(3) the neutralization and water washing steps are reduced, the wastewater amount is reduced, the production time is reduced, and the production cost is reduced
(4) The use of active carbon is greatly reduced, the generation of hazardous waste is reduced, and the environmental protection pressure is reduced;
in order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of phthalate plasticizer is characterized by comprising the steps of esterification, crude dealcoholization, cooling and deacidification agent addition, dealcoholization and filtration;
the esterification is carried out by adopting a reaction of dibasic acid or anhydride and monohydric alcohol, wherein the molar ratio of the dibasic acid or anhydride to the alcohol is 1: 2.2-2.8;
preferably, the molar ratio of phthalic anhydride to secondary octanol is 1: 2.5-2.6; the catalyst accounts for 5.0-5.8% of the total amount of the reaction materials; the esterification reaction temperature is 200-210 ℃, and the heating is stopped when the acid value of the reaction system is less than or equal to 1.0 mgKOH/g;
the catalyst is an ion exchange resin immobilized catalyst, in particular to a high-temperature resistant macroporous strong-acid styrene cation exchange resin, the total exchange capacity is 5.2-6.0mmol/g, and the specific surface area is 50-60m 2/g;
the coarse dealcoholization is carried out, and nitrogen is replaced until the oxygen content in the kettle is 0-0.5%; keeping the vacuum degree at 0.1MPa, and stopping heating when the final temperature of the crude dealcoholization reaches 160 ℃;
the deacidification agent is added after the temperature is reduced, and the adding amount of the deacidification agent accounts for 5-8% of the mass of the materials; columnar particles;
the deacidification agent comprises the following components in percentage by weight: 10-15% of metal oxide, 55-60% of calcium oxide, 20-25% of kaolin and 5-10% of silica sol;
the metal oxide comprises one or more of zinc oxide, magnesium oxide and aluminum oxide;
the deacidification agent has the functions of accelerating the decomposition of colored substances and acidic substances in the materials and simultaneously playing a role in neutralizing the residual acidic impurities;
the deacidification agent is added, the temperature is reduced to 80-90 ℃ in the kettle, and the deacidification agent is added in a mode of pressing in by adopting a diaphragm pump;
the dealcoholization comprises the steps of firstly reducing the pressure in the kettle to-0.089-0.095 Mpa, raising the temperature to 150-;
the steam stripping is carried out for 15-20 min;
the di-sec-octyl phthalate prepared by the preparation method has the color number of 10-15#, the acid value of less than or equal to 0.05mgKOH/g, the water content of less than or equal to 0.05 percent, the content of more than or equal to 99.5 percent and the alcohol content of less than or equal to 0.005 percent.
The invention adopts the ion exchange resin immobilized acid-base catalyst to catalyze the esterification reaction, and strictly controls parameters such as system temperature, deacidification agent addition amount, stripping pressure and the like, thereby avoiding the occurrence of saponification reaction, facilitating the precipitation and separation of the deacidification agent and impurities, having simple preparation process, high raw material conversion rate and high product purity, and being suitable for large-scale popularization and use.
By adopting the technical scheme, the invention has the beneficial effects that:
1. by adopting the preparation method, the decoloring agent treatment is not needed, the chromaticity of the prepared phthalate plasticizer product reaches 10-15# through platinum-cobalt standard color comparison, and 5.75-11.12# through detection of a Hunlexlab easy match QC color difference instrument, and the product has higher transparency and better color number compared with the conventional production method;
2. by adopting the preparation method, the acid value of the prepared phthalate plasticizer product is reduced to 0.019-0.042 mgKOH/g, and the ester content reaches 99.72-99.90%;
3. by adopting the preparation method of the invention, the alcohol content of the prepared phthalate plasticizer product is lower,
the alcohol content reaches 0.0011 to 0.0032 percent;
4. by adopting the method, the neutralization and washing are not needed, the steps of production links are reduced, the investment of related equipment is further reduced, and the production cost and the wastewater production are greatly reduced;
5. by adopting the method, active carbon and other decolorants are not required to be added, and the generation amount of hazardous waste is reduced. Saving production cost
6. By adopting the method, the production links are reduced, the alkaline washing, water washing and settling time is saved, the production time is greatly reduced, the production yield in unit time is improved, and the production benefit is increased.
The specific implementation mode is as follows:
the invention is further illustrated below with reference to specific examples.
EXAMPLE 1 preparation of phthalate plasticizer
A method for preparing di-sec-octyl phthalate as phthalate plasticizer comprises 5 steps of esterification, crude dealcoholization, cooling and deacidification agent addition, dealcoholization and filtration;
1. esterification
Adding phthalic anhydride and secondary octanol into a reaction kettle according to a molar ratio of 1:2.5, simultaneously adding a resin catalyst in a proportion of 5.0% relative to the total mass of reaction materials into the reaction kettle, then starting heating and stirring, keeping the esterification reflux temperature at 200 ℃, and stopping heating when the acid value of a reaction system is 0.92 mgKOH/g;
the resin catalyst is high-temperature resistant macroporous strong-acid styrene cation exchange resin, the total exchange capacity is 5.2mmol/g, and the specific surface area is 51m 2/g;
2. crude dealcoholization
And (3) replacing the dealcoholization kettle for 5 minutes by using nitrogen, detecting and replacing the oxygen content in the detection device to be less than 0.5%, pumping the reacted di-sec-octyl phthalate esterified material into the dealcoholization kettle from the reaction kettle by using a material pump, keeping the dealcoholization kettle in a negative pressure state and keeping the vacuum degree at 0.1MPa in the crude dealcoholization process, and preliminarily removing most of unreacted sec-octanol in the esterified material. The crude dealcoholization reaches the final temperature of 160 ℃, the heating is stopped, and the residual temperature is raised to 170 ℃;
3. cooling and deacidifying agent
Stopping heating the dealcoholization kettle when the temperature in the dealcoholization kettle begins to rise and the heating rate is 10 ℃/min, cooling the materials in the dealcoholization kettle by adopting circulating water, reducing the temperature in the dealcoholization kettle to 90 ℃, and then adding a deacidification agent into the dealcoholization kettle;
the deacidification agent comprises the following components in percentage by weight: 10% of zinc oxide, 60% of calcium oxide, 25% of kaolin and 5% of silica sol;
the addition amount of the deacidification agent is 5 percent of the mass of the material;
the deacidification agent is columnar particles, and is added in a mode of being pressed in by adopting a diaphragm pump;
4. dealcoholization
Rapidly starting a vacuum pump after adding a deacidification agent, controlling the pressure in the dealcoholization kettle to be-0.095 Mpa, then introducing steam to heat the materials in the dealcoholization kettle, controlling the heating rate to be 10 ℃/min, introducing 0.2Mpa of steam into the dealcoholization kettle to strip the materials in the dealcoholization kettle after the materials in the dealcoholization kettle reach 170 ℃, and controlling the stripping time to be 15 min;
in the stage, the decomposition of colored substances and acidic substances in the materials is accelerated through the catalytic action, the generation of calcium hydroxide from water vapor and calcium oxide is accelerated, and the calcium hydroxide neutralizes and removes the residual acidic substances, so that the decolorization and deacidification are realized;
5. filtration
And filtering the material in a filter pressing mode after the material is detected to be qualified, pressing the finished product material into a finished product tank with nitrogen protection from a dealcoholization kettle for later use, and continuously reusing the deacidification agent until the deacidification agent is invalid.
The detection indexes of the di-sec-octyl phthalate prepared by adopting the technical scheme of the embodiment 1 are as follows:
example 2: preparation method of phthalate plasticizer
1. Esterification
Adding phthalic anhydride and octanol into a reaction kettle according to a molar ratio of 1:2.55 for esterification reaction, simultaneously adding a resin catalyst which accounts for 5.5 percent of the total mass of reaction materials into the reaction kettle, then starting heating and stirring, keeping the esterification reflux temperature at 200 ℃, and stopping the reaction when the acid value of a reaction system is 0.95 mgKOH/g;
the resin catalyst is high-temperature resistant macroporous strong-acid styrene cation exchange resin, the total exchange capacity is 5.5mmol/g, and the specific surface area is 53m 2/g;
2. crude dealcoholization
Replacing the dealcoholization kettle with nitrogen for 5 minutes, detecting and detecting that the oxygen content in the detection device is less than 0.5% after replacement, pumping the reacted di-sec-octyl phthalate esterified material into the dealcoholization kettle from the reaction kettle by using a material pump, keeping the dealcoholization kettle in a negative pressure state and a vacuum degree of 0.1MPa in the course of coarse dealcoholization, preliminarily removing most of unreacted sec-octanol in the esterified material, stopping heating when the coarse dealcoholization reaches a final temperature of 160 ℃, and raising the residual temperature to 170 ℃;
3. cooling and deacidifying agent
When the temperature in the dealcoholization kettle begins to rise and the temperature rise rate is 8 ℃/min, stopping heating the dealcoholization kettle. Cooling the materials in the dealcoholization kettle by using circulating water, reducing the temperature in the dealcoholization kettle to 85 ℃, and adding a deacidification agent into the dealcoholization kettle;
the deacidification agent comprises the following components in percentage by weight: 13% of magnesium oxide, 56% of calcium oxide, 23% of kaolin and 8% of silica sol;
the addition amount of the deacidification agent is 7 percent of the mass of the material;
the deacidification agent is columnar particles, and is added in a mode of being pressed in by adopting a diaphragm pump;
4. dealcoholization
Rapidly starting a vacuum pump after adding a deacidification agent, controlling the pressure in the dealcoholization kettle to be-0.092 Mpa, then introducing steam to heat the materials in the dealcoholization kettle, controlling the heating rate to be 10 ℃/min, introducing 0.15Mpa of steam into the dealcoholization kettle to strip the materials in the dealcoholization kettle after the materials in the dealcoholization kettle reach 160 ℃, and controlling the stripping time to be 18 min;
in the stage, the decomposition of colored substances and acidic substances in the materials is accelerated through the catalytic action, the generation of calcium hydroxide from water vapor and calcium oxide is accelerated, and the calcium hydroxide neutralizes and removes the residual acidic substances, so that the decolorization and deacidification are realized;
5. filtration
And filtering the material in a filter pressing mode after the material is detected to be qualified, pressing the finished product material into a finished product tank with nitrogen protection from a dealcoholization kettle for later use, and continuously reusing the deacidification agent until the deacidification agent is invalid.
The detection indexes of the di-sec-octyl phthalate prepared by adopting the technical scheme of the embodiment 2 are as follows:
example 3: preparation method of phthalate plasticizer
1. Esterification
Adding phthalic anhydride and n-butyl alcohol into a reaction kettle according to the molar ratio of 1:2.6 for esterification reaction, simultaneously adding a resin catalyst in a proportion of 5.8 percent relative to the total mass of reaction materials into the reaction kettle, then starting heating and stirring, keeping the esterification reflux temperature at 200 ℃ and 210 ℃, and stopping the reaction when the acid value of the materials reaches 0.90 mgKOH/g;
the resin catalyst is high-temperature resistant macroporous strong-acid styrene cation exchange resin, the total exchange capacity is 5.8mmol/g, and the specific surface area is 56m 2/g;
2. crude dealcoholization
Replacing the dealcoholization kettle with nitrogen for 5 minutes, detecting and detecting that the oxygen content in the detection device is less than 0.5% after replacement, pumping the reacted di-sec-octyl phthalate esterified material into the dealcoholization kettle from the reaction kettle by using a material pump, keeping the dealcoholization kettle in a negative pressure state and a vacuum degree of 0.1MPa in the course of coarse dealcoholization, preliminarily removing most of unreacted sec-octanol in the esterified material, stopping heating when the coarse dealcoholization reaches a final temperature of 150 ℃, and raising the residual temperature to 170 ℃;
3. cooling and deacidifying agent
When the temperature in the dealcoholization kettle begins to rise and the temperature rise rate is 5 ℃/min, stopping heating the dealcoholization kettle. Cooling the materials in the dealcoholization kettle by using circulating water, and adding a deacidification agent into the dealcoholization kettle when the temperature in the dealcoholization kettle is reduced to 80 ℃;
the deacidification agent comprises the following components in percentage by weight: 15% of alumina, 55% of calcium oxide, 20% of kaolin and 10% of silica sol;
the addition amount of the deacidification agent is 8 percent of the mass of the material;
the deacidification agent is columnar particles, and is added in a mode of being pressed in by adopting a diaphragm pump;
4. dealcoholization
Rapidly starting a vacuum pump after adding a deacidification agent, controlling the pressure in the dealcoholization kettle to be-0.089 Mpa, then introducing steam to heat the materials in the dealcoholization kettle, controlling the heating rate to be 10 ℃/min, introducing 0.1Mpa of steam into the dealcoholization kettle to strip the materials in the dealcoholization kettle after the materials in the dealcoholization kettle reach 150 ℃, and controlling the stripping time to be 20 min;
5. filtration
And filtering the material in a filter pressing mode after the material is detected to be qualified, pressing the finished product material into a finished product tank with nitrogen protection from a dealcoholization kettle for later use, and continuously reusing the deacidification agent until the deacidification agent is invalid.
The detection indexes of the di-sec-octyl phthalate prepared by adopting the technical scheme of the embodiment 3 are as follows:
through detection, the invention obtains the technical indexes of the product: the appearance is colorless transparent liquid, the color number is less than or equal to 15#, the acid value is less than or equal to 0.05mgKOH/g, the water content is less than or equal to 0.05 percent, the content is more than or equal to 99.5 percent, and the alcohol content is less than or equal to 0.005 percent; in addition, in the preparation process, activated carbon is not used in the esterification process, a deacidification agent is used for destroying colored substances and acidic substances generated in the esterification reaction, a small amount of secondary octanol in the material during crude dealcoholization is removed with water in the deacidification agent through steam stripping, steam and calcium oxide react in the dealcoholization process to generate calcium hydroxide, unconverted acidic substances are neutralized and removed, the neutralization and water washing steps are reduced, and the amount of wastewater is reduced; meanwhile, the contact area between materials is large, the reaction rate is high, the conversion rate of raw materials is high, the product purity is high, the conversion rate of acid or acid anhydride can reach more than 99.0 percent, and the advantages of the production process are very obvious.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of phthalate plasticizer is characterized by comprising the steps of esterification, crude dealcoholization, cooling and deacidification agent addition, dealcoholization and filtration; and in the esterification, dibasic acid or anhydride is adopted to react with monohydric alcohol, and the molar ratio of the dibasic acid or anhydride to the alcohol is 1: 2.2-2.8.
2. The method of claim 1, wherein said esterification, phthalic anhydride to secondary octanol molar ratio is 1: 2.5-2.6; the catalyst accounts for 5.0-5.8% of the total amount of the reaction materials; the esterification reaction temperature is 200-210 ℃, and the heating is stopped when the acid value of the reaction system is less than or equal to 1.0 mgKOH/g.
3. The preparation method of claim 2, wherein the catalyst is a high-temperature resistant macroporous strongly acidic styrene cation exchange resin, the total exchange capacity is 5.2-6.0mmol/g, and the specific surface area is 50-60m 2/g.
4. The preparation method of claim 1, wherein the cooling deacidification agent is added in an amount of 5-8% by mass of the material.
5. The preparation method according to claim 4, wherein the deacidification agent comprises the following components in percentage by weight: 10-15% of metal oxide, 55-60% of calcium oxide, 20-25% of kaolin and 5-10% of silica sol; the metal oxide comprises one or more of zinc oxide, magnesium oxide and aluminum oxide.
6. The preparation method according to claim 4, wherein the temperature of the deacidification agent is reduced to 80-90 ℃.
7. The process of claim 1, wherein the dealcoholization comprises reducing the pressure in the reactor to-0.089 to-0.095 MPa, raising the temperature at a rate of 8 to 10 ℃/min to 15 · 0 to 170 ℃, and then stripping with steam of 0.1 to 0.2 MPa.
8. The method of claim 6, wherein the stripping is carried out for a period of 15-20 min.
9. The method of claim 1, wherein the crude dealcoholization has an oxygen content in the kettle of 0 to 0.5%; keeping the vacuum degree at 0.1MPa, and stopping heating when the final temperature of the crude dealcoholization reaches 160 ℃.
10. The preparation method of claim 1, wherein the obtained di-sec-octyl phthalate has a color number of 10-15#, an acid value of less than or equal to 0.05mgKOH/g, a water content of less than or equal to 0.05%, a content of greater than or equal to 99.5%, and an alcohol content of less than or equal to 0.005%.
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| CN112592273A (en) * | 2020-12-30 | 2021-04-02 | 河南庆安化工高科技股份有限公司 | Production process of phthalate plasticizer |
| CN113214079A (en) * | 2021-05-26 | 2021-08-06 | 浙江皇星化工股份有限公司 | Production method of DPHP |
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| CN113214079A (en) * | 2021-05-26 | 2021-08-06 | 浙江皇星化工股份有限公司 | Production method of DPHP |
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