CN106588649A - Continuous catalyzing method for preparing bivalent acid ester plasticizer - Google Patents
Continuous catalyzing method for preparing bivalent acid ester plasticizer Download PDFInfo
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- CN106588649A CN106588649A CN201611134038.3A CN201611134038A CN106588649A CN 106588649 A CN106588649 A CN 106588649A CN 201611134038 A CN201611134038 A CN 201611134038A CN 106588649 A CN106588649 A CN 106588649A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a continuous catalyzing method for preparing a bivalent acid ester plasticizer. The continuous catalyzing method comprises the following steps of continuously catalyzing and esterifying, performing alkali washing and neutralizing, and removing high boiling fraction. In the step of continuously catalyzing and esterifying, a hydrated cerium sulphate catalyst is added into raw materials, the temperature is increased to 120 to 145 DEG C, the pressure is kept at 125 to 201 KPa, and the hydrated cerium sulphate catalyst reacts with the raw materials for 1 to 2 hours; methanol is continuously added, wherein the adding amount is 143 to 165 percent of the first methanol adding amount, the temperature is increased to 130 to 160 DEG C, and the temperature is kept unchanged; and a titanate catalyst is added, wherein the adding amount is 0.82 to 1.05 percent of the total amount of a reaction product; when the acid value is lower than 5 mg KOH/g, the temperature is quickly reduced to 65 to 85 DEG C; after the product prepared by the method which is provided by the invention is placed for one year, the acid value is basically kept unchanged and does not return to be acidic; and the product purity is 99.82 to 99.96 percent, the content of methanol is 0.008 to 0.03 percent, and the content of a mono-methyl ester is 0.0003 to 0.0021 percent.
Description
Technical field
The present invention relates to a kind of method of the continuous catalysis for preparing divalent acid ester plasticizer, belongs to lactate synthesis technology neck
Domain.
Background technology
Dibasic ester, is commonly called as MDBE, nylon acid methyl esters, is a kind of higher boiling environmentally friendly solvent, and Du Pont name DBE, first promise is ordered
Name DME, domestic also known as NME.The mixture that NME is made up of three kinds of dibasic esters, is by butanedioic acid（Dimethyl succinate
CH3OOC（CH2）2COOCH3, dimethyl glutarate CH3OOC（CH2）3COOCH3With hexanedioic acid dimethyl ester CH3OOC（CH2）4COOCH3
The combination of three kinds of good environment solvents, just because of this unique composition, makes NME become a kind of nontoxic, water white liquid
Body, the fragranced for having light ester, with superpower solvability, is that biodegradable environment protection type high-boiling-point solvent is widely used in vapour
The industry such as car coating, color steel sheet coating, can lacquer, enamel-covered wire and family's electrical materials and appliances, furniture woodwork coating.
At present, NME products are first by the same binary acid for mixing of methyl alcohol in production（Nylon acid）In a kind of catalysis of catalyst
Lower reaction, then rectifying is separated into different products.But the impurity content, methanol content in NME is all universal higher, does not reach
Some demands of high-grade, precision and advanced field to such product, also less high in terms of selectivity, conversion ratio, the colourity and acid number of product
It is not ideal, it is therefore desirable to research and develop a kind of high product preparation method of purity.
In sum, the production method of prior art, has the following disadvantages：
（1）Reactant reaction is insufficient, and selective, conversion ratio is low, causes the waste of raw material；
（2）Target product purity does not reach the requirement in some high-grade, precision and advanced fields, particularly acid number, methanol content and single ester impurities
Content is universal not low enough；
（3）The heat time is long in reaction, and energy resource consumption is high；
（4）Catalyst used in reaction, is not sufficiently stable, safety during use, and easily poisoning easily produces corrosion to equipment.
The content of the invention
The present invention is solution above technical problem, there is provided a kind of side of the continuous catalysis for preparing divalent acid ester plasticizer
Method, especially for the continuous catalytic method of divalent acid dimethyl ester plasticizer, reaction equation is as follows：
To realize following goal of the invention：
（1）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, can improve reaction conversion ratio and
It is selective；
（2）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the product purity for obtaining is high, acid number
Low, methanol content is low, monoesters class impurity content is low；
（3）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, can reduce the heat time, reduce energy
Source consumes, and product will not cause colourity to deepen because of heated time length；
（4）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the catalyst for being used can be followed repeatedly
Ring is used, and stable during use, safety, repeat performance is good, is difficult poisoning, and corrosion will not be produced to equipment, right
Environment does not produce pollution, belongs to green catalyst；
（5）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the reaction condition of continuous catalysis esterification
Gently it is easily controlled, reaction process is simple to operation.
To solve above technical problem, the technical solution used in the present invention is as follows：
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer, comprises the following steps：In continuous catalysis esterification, alkali cleaning
With with de- heavy step.
The continuous catalysis esterification, including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：The mass ratio of nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.3-1.6：0.02-
0.05 weighs each raw material, adds aqueous sulfuric acid cerium catalyst, is heated to 120-145 DEG C, and pressure is 125-201Kpa, reacts 1-2
Hour；
Second catalytic esterification of b：The mode for taking continuous logical alcohol continues reaction, reacts the water methyl alcohol band for generating and sends as an envoy to and reacts
To continue, addition is the 143-165% of methyl alcohol addition in first time catalytic esterification, and this stage of reaction is synthesis under normal pressure, is passed through
The speed that is passed through of control methyl alcohol carrys out controlling reaction temperature, is heated to 130-160 DEG C, and keeping temperature is constant, adds titanate ester to urge
Agent, addition is the 8.2-10.5 ‰ of reactant gross mass, when acid number is reached less than 5mgKOH/g, 65- is cooled to rapidly
85 DEG C, stop reaction.
The aqueous sulfuric acid cerium catalyst, be made up of cerous sulfate active component and double mesoporous silicon carriers, wherein cerous sulfate
Mass percent is 42-50%, balance of double mesoporous.
In 3-5nm, big mesoporous aperture is in 10-15nm in the described pair of mesoporous silicon little mesoporous aperture.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, metatitanic acid
The mass ratio of tetra-ethyl ester, metatitanic acid orthocarbonate and tetraisopropyl titanate is 2:5-8:3.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, metatitanic acid
The optimum quality ratio of tetra-ethyl ester, metatitanic acid orthocarbonate and tetraisopropyl titanate is 2:6-7:3.
Second catalytic esterification, titanate ester catalyst charge is the 9.4-9.8 ‰ of reactant gross mass.
The alkali cleaning neutralization, at 85-95 DEG C, with 20% NaHCO3Stir while adding, stir speed (S.S.) is 100-
160rad/min, when the acid number of crude product is less than 0.5-1.0mgKOH/g, stops adding, and continues to stir 10-15min.
The de- heavy step, the pressure in weight-removing column is -0.085 to -0.02MPa, and tower top temperature is 113-135 DEG C, tower
Bottom temperature is 150-160 DEG C, and reflux ratio is set to 0.7-2.1.
The product that a kind of method of the continuous catalysis for preparing divalent acid ester plasticizer is obtained, purity is 99.82-
99.96%, the content of methyl alcohol is 0.008-0.03%, and mono-methyl content is 0.003-0.021 ‰.
Using above technical scheme, compared with the method for the prior art, the present invention has the beneficial effect that：
（1）Using the inventive method, conversion ratio and the selectivity of reaction are improve；The conversion ratio of reaction reaches 99.64-99.81%,
The selectivity of reaction is 99.83-99.96%；
（2）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the product quality for obtaining is high：Purity
Height, acid number is low, and methanol content is low, monoesters class impurity content is low；Purity is 99.82-99.96%, and the acid number of product is 0.10-
0.04mgKOH/g；Wherein, the content of methyl alcohol is 0.008-0.03%, and mono-methyl content is 0.003-0.021 ‰；
（3）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, reduces the heat time, reduces energy
Source consumes, and product will not cause colourity to deepen because of heated time length；Product color is stablized, and colourity is light color system；
（4）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the catalyst for being used can be followed repeatedly
Ring is used, and stable during use, safety, repeat performance is good, after catalyst uses 30-44 time, activity decrease degree
Less than 10%, poisoning is difficult, and corrosion will not be produced to equipment, pollution is not produced to environment, be green catalyst.
（5）The method that the continuous catalysis of divalent acid ester plasticizer are prepared using the present invention, the reaction of continuous catalysis esterification
Mild condition is easily controlled, and reaction process is simple to operation；The reaction condition pressure of continuous catalysis esterification is 125-201KPa, warm
At 120-160 DEG C, low to the pouring of equipment, technological parameter is easily controlled degree.
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Specifically describe the present invention in the form of embodiment below：
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer of embodiment 1
Comprise the following steps：
（1）Continuous catalysis are esterified
Including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：Mass ratio according to nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.3：0.02 weighs
Each raw material, feedstock nylon acid and methyl alcohol are added sequentially in reactor, are subsequently adding aqueous sulfuric acid cerium catalyst, while stirring
Heating, is heated to 120 DEG C, and keeping temperature is constant, and it is 125KPa to control the pressure inside reactor, is reacted 1 hour；
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
Percentage is 42%, balance of double mesoporous；In 3-5nm, big mesoporous aperture is in 10- in the described pair of mesoporous silicon little mesoporous aperture
15nm。
Second catalytic esterification of b：Reacted by the way of methyl alcohol using being continuously passed through in reactor, react the water for generating
Continued with the reaction of sening as an envoy to of methyl alcohol band, methyl alcohol addition is 143% of methyl alcohol addition in first time catalytic esterification, this reaction
Stage is synthesis under normal pressure, and speed is passed through come controlling reaction temperature by control methyl alcohol, and the reaction temperature in this stage is 130 DEG C,
Keeping temperature is invariable, adds titanate ester catalyst, addition to be the 8.2 ‰ of reactant gross mass, reacts 5 hours, surveys
Its acid number is measured, when acid number is reached less than 5mgKOH/g, 65 DEG C is cooled to rapidly, stop reaction, obtain crude product.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, quality
Than for 2:5:3.
（2）Alkali cleaning is neutralized
Removing catalyst is separated by filtration, 20% NaHCO is slowly added to in the crude product of reactor3, in the case where temperature is for 85 DEG C,
Stirred with the speed of 100rad/min when adding, when the acid number of crude product is less than 0.5mgKOH/g, stop adding, continue to stir
Mix 10min；
The catalyst being separated off is recycled after simple process, records access times.
（3）Stand at low temperature
Above-mentioned product is placed in into environment temperature to stand at -3 DEG C, after standing 25min, water-yielding stratum is separated after layering, remove moisture.
（4）Crude product materials pump after eliminating water is got in lightness-removing column, -0.01MPa is decompressed to, tower top temperature is arranged and arrived
105 DEG C, light component is sloughed, the methyl alcohol Jing dehydrating and removing impurities Posterior circle in light component to catalytic esterification kettle is recycled；
The packing layer being provided with the lightness-removing column uses polypropylene plastics cascade ring, a diameter of 50mm of cascade ring used,
Top is using backflow in tubulation.
（5）The crude product for sloughing light component is put in weight-removing column, decompression operation is sloughing heavy constituent；Pressure control after decompression
- 0.085MPa is made as, the tower top temperature of weight-removing column is controlled to 125 DEG C, and column bottom temperature is controlled to 150 DEG C, and reflux ratio is set to 0.7,
Collect product at tower top.
Through the product that said method process is obtained, after testing, product color is stable, and colourity is light color system, colourity difference
Less, main component is NME（The mixture of dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three）, NME's
Purity is 99.82%, wherein, the content of methyl alcohol is 0.021%, and mono-methyl content is 0.012 ‰；
Quality analyses of the Jing to each composition before and after reaction, up to 99.64%, the selectivity of reaction is for the conversion ratio of reaction
99.83%；
The acid number of product is 0.14mgKOH/g；
The moisture of product is 0.020%；
Using after 30 times, activity decrease degree is less than 10% to catalyst, and stable during use, repeat performance is good, is difficult
Poisoning, will not etching apparatus, pollution is not produced to environment.
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer of embodiment 2
（1）Continuous catalysis are esterified
Including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：Mass ratio according to nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1：1.53：0.04 claims
Each raw material is taken, feedstock nylon acid and methyl alcohol are added sequentially in reactor, be subsequently adding aqueous sulfuric acid cerium catalyst, side stirring
Side is heated, and is heated to 130 DEG C, and keeping temperature is constant, and it is 135KPa to control the pressure inside reactor, is reacted 1.8 hours；
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
Percentage is 47%, balance of double mesoporous；In 3-5nm, big mesoporous aperture is in 10- in the described pair of mesoporous silicon little mesoporous aperture
15nm。
Second catalytic esterification of b：Reacted by the way of methyl alcohol using being continuously passed through in reactor, methyl alcohol addition is
The 162% of methyl alcohol addition in first time catalytic esterification, this stage of reaction is synthesis under normal pressure, and by control methyl alcohol speed is passed through
Carry out controlling reaction temperature, the reaction temperature in this stage is 140 DEG C, and keeping temperature is invariable, add titanate ester catalyst, plus
Enter amount be reactant gross mass 9.8 ‰, react 5.6 hours, measure its acid number, when acid number reaches 4.5mgKOH/g, rapidly
75 DEG C are cooled to, stop reaction, obtain crude product.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, quality
Than for 2:7:3.
（2）Alkali cleaning is neutralized
Removing catalyst is separated by filtration, 20% NaHCO is slowly added to in the crude product of reactor3, in the case where temperature is for 92 DEG C,
Stirred with the speed of 155rad/min when adding, when the acid number of crude product is 4.6mgKOH/g, stop adding, continue to stir
10-15min；
The catalyst being separated off is recycled after simple process, records access times.
（3）Stand at low temperature
Above-mentioned product is placed in into environment temperature to stand at 7.5 DEG C, after standing 31min, water-yielding stratum is separated after layering, remove water
Point.
（4）Crude product after eliminating water is added in lightness-removing column, -0.025MPa is decompressed to, tower top temperature is 95 DEG C, sloughed light
Component, the methyl alcohol Jing dehydrating and removing impurities Posterior circle in light component to catalytic esterification kettle is recycled；
The packing layer being provided with the lightness-removing column uses polypropylene plastics cascade ring, a diameter of 65mm of cascade ring used,
Top is using backflow in tubulation.
（5）The crude product for sloughing light component is put in weight-removing column, decompression operation is sloughing heavy constituent；Be decompressed to-
0.075MPa, the tower top temperature of weight-removing column is controlled to 130 DEG C, and column bottom temperature is controlled to 155 DEG C, and reflux ratio is set to 2.0, collects tower
Product at top.
Through the product that said method process is obtained, after testing, product color is stable, and colourity is light color system, colourity difference
Less, main component is NME（The mixture of dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three）, NME's
Purity is 99.96%, wherein, the content of methyl alcohol is 0.029%, and mono-methyl content is 0.003 ‰；
Quality analyses of the Jing to each composition before and after reaction, up to 99.80%, the selectivity of reaction is for the conversion ratio of reaction
99.96%；
The acid number of product is 0.11mgKOH/g；
The moisture of product is 0.011%；
Using after 44 times, activity decrease degree is less than 10% to catalyst, and stable during use, repeat performance is good, is difficult
Poisoning, will not etching apparatus, pollution is not produced to environment.
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer of embodiment 3
Comprise the following steps：
（1）Continuous catalysis are esterified
Including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：Mass ratio according to nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.5：0.03 weighs
Each raw material, feedstock nylon acid and methyl alcohol are added sequentially in reactor, are subsequently adding aqueous sulfuric acid cerium catalyst, while stirring
Heating, is heated to 137 DEG C, and keeping temperature is constant, and it is 140KPa to control the pressure inside reactor, is reacted 1.4 hours；
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
Percentage is 46%, balance of double mesoporous；In 3-5nm, big mesoporous aperture is in 10- in the described pair of mesoporous silicon little mesoporous aperture
15nm。
Second catalytic esterification of b：Reacted by the way of methyl alcohol using being continuously passed through in reactor, methyl alcohol addition is
The 162% of methyl alcohol addition in first time catalytic esterification, this stage of reaction is synthesis under normal pressure, and by control methyl alcohol speed is passed through
Carry out controlling reaction temperature, the reaction temperature in this stage is 144 DEG C, and keeping temperature is invariable, add titanate ester catalyst, plus
Enter amount be reactant gross mass 9.4 ‰, react 6.1 hours, measure its acid number, when acid number reaches 4.8mgKOH/g, rapidly
79 DEG C are cooled to, stop reaction, obtain crude product.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, quality
Than for 2:7:3.
（2）Alkali cleaning is neutralized
Removing catalyst is separated by filtration, 20% NaHCO is slowly added to in the crude product of reactor3, in the case where temperature is for 90 DEG C,
Stirred with the speed of 130rad/min when adding, when the acid number of crude product is less than 2.2mgKOH/g, stop adding, continue to stir
Mix 12min；
The catalyst being separated off is recycled after simple process, records access times.
（3）Stand at low temperature
Above-mentioned product is placed in into environment temperature to stand at 3.5 DEG C, after standing 30min, water-yielding stratum is separated after layering, remove water
Point.
（4）Crude product after eliminating water is added in lightness-removing column, -0.026MPa is decompressed to, tower top temperature is arranged to 95 DEG C, is taken off
Light component is gone, the methyl alcohol Jing dehydrating and removing impurities Posterior circle in light component to catalytic esterification kettle is recycled；
The packing layer being provided with the lightness-removing column uses polypropylene plastics cascade ring, a diameter of 55mm of cascade ring used,
Top is using backflow in tubulation.
（5）The crude product for sloughing light component is put in weight-removing column, decompression operation is sloughing heavy constituent；Pressure after decompression
For -0.077MPa, the tower top temperature of weight-removing column is controlled to 113 DEG C, and column bottom temperature is controlled to 159 DEG C, and reflux ratio is set to 1.4, receives
Product at collection tower top.
Through the product that said method process is obtained, after testing, product color is stable, and colourity is light color system, colourity difference
Less, main component is NME（The mixture of dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three）, NME's
Purity is 99.96%, wherein, the content of methyl alcohol is 0.021%, and mono-methyl content is 0.006 ‰；
Quality analyses of the Jing to each composition before and after reaction, up to 99.81%, the selectivity of reaction is for the conversion ratio of reaction
99.95%；
The acid number of product is 0.10mgKOH/g；
The moisture of product is 0.011%；
Using after 42 times, activity decrease degree is less than 10% to catalyst, and stable during use, repeat performance is good, is difficult
Poisoning, will not etching apparatus, pollution is not produced to environment.
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer of embodiment 4
Comprise the following steps：
（1）Continuous catalysis are esterified
Including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：Mass ratio according to nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.4：0.03 weighs
Each raw material, feedstock nylon acid and methyl alcohol are added sequentially in reactor, are subsequently adding aqueous sulfuric acid cerium catalyst, while stirring
Heating, is heated to 134 DEG C, and keeping temperature is constant, and it is 201KPa to control the pressure inside reactor, is reacted 1 hour；
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
Percentage is 43.2%, balance of double mesoporous；In 3-5nm, big mesoporous aperture is in 10- in the described pair of mesoporous silicon little mesoporous aperture
15nm。
Second catalytic esterification of b：Reacted by the way of methyl alcohol using being continuously passed through in reactor, methyl alcohol addition is
The 155% of methyl alcohol addition in first time catalytic esterification, this stage of reaction is synthesis under normal pressure, and by control methyl alcohol speed is passed through
Carry out controlling reaction temperature, the reaction temperature in this stage is 147 DEG C, and keeping temperature is invariable, add titanate ester catalyst, plus
Enter amount be reactant gross mass 9.3 ‰, react 5.7 hours, measure its acid number, when acid number reaches 4.0mgKOH/g, rapidly
82 DEG C are cooled to, stop reaction, obtain crude product.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, quality
Than for 2:6:3.
（2）Alkali cleaning is neutralized
Removing catalyst is separated by filtration, 20% NaHCO is slowly added to in the crude product of reactor3, in the case where temperature is for 89 DEG C,
Stirred with the speed of 105rad/min when adding, when the acid number of crude product is less than 0.9mgKOH/g, stop adding, continue to stir
Mix 10-15min；
The catalyst being separated off is recycled after simple process, records access times.
（3）Stand at low temperature
Above-mentioned product is placed in into environment temperature to stand at 0 DEG C, after standing 28min, water-yielding stratum is separated after layering, remove moisture.
（4）Crude product after eliminating water is added in lightness-removing column, 0.02MPa is decompressed to, tower top temperature is arranged to 175 DEG C, is taken off
Light component is gone, the methyl alcohol Jing dehydrating and removing impurities Posterior circle in light component to catalytic esterification kettle is recycled；
The packing layer being provided with the lightness-removing column uses polypropylene plastics cascade ring, a diameter of 55mm of cascade ring used,
Top is using backflow in tubulation.
（5）The crude product for sloughing light component is put in weight-removing column, decompression operation is sloughing heavy constituent；Pressure control after decompression
- 0.02MPa is made as, the tower top temperature of weight-removing column is controlled to 175 DEG C, and column bottom temperature is controlled to 155 DEG C, and reflux ratio is set to 0.8, receives
Product at collection tower top.
Through the product that said method process is obtained, after testing, product color is stable, and colourity is light color system, colourity difference
Less, main component is NME（The mixture of dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three）, NME's
Purity is 99.89%, wherein, the content of methyl alcohol is 0.019%, and mono-methyl content is 0.017 ‰；
Quality analyses of the Jing to each composition before and after reaction, up to 99.72%, the selectivity of reaction is for the conversion ratio of reaction
99.85%；
The acid number of product is 0.13mgKOH/g；
The moisture of product is 0.018%；
Using after 38 times, activity decrease degree is less than 10% to catalyst, and stable during use, repeat performance is good, is difficult
Poisoning, will not etching apparatus, pollution is not produced to environment.
A kind of method of the continuous catalysis for preparing divalent acid ester plasticizer of embodiment 5
Comprise the following steps：
（1）Continuous catalysis are esterified
Including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：Mass ratio according to nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.6：0.05 weighs
Each raw material, feedstock nylon acid and methyl alcohol are added sequentially in reactor, are subsequently adding aqueous sulfuric acid cerium catalyst, while stirring
Heating, is heated to 145 DEG C, and keeping temperature is constant, and it is 195KPa to control the pressure inside reactor, is reacted 2.1 hours；
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
Percentage is 50%, balance of double mesoporous；In 3-5nm, big mesoporous aperture is in 10- in the described pair of mesoporous silicon little mesoporous aperture
15nm。
Second catalytic esterification of b：Reacted by the way of methyl alcohol using being continuously passed through in reactor, methyl alcohol addition is
The 174% of methyl alcohol addition in first time catalytic esterification, this stage of reaction is synthesis under normal pressure, and by control methyl alcohol speed is passed through
Carry out controlling reaction temperature, the reaction temperature in this stage is 160 DEG C, and keeping temperature is invariable, add titanate ester catalyst, plus
Enter amount be reactant gross mass 10.4 ‰, react 5.8 hours, measure its acid number, when acid number reaches 3.8mgKOH/g, rapidly
85 DEG C are cooled to, stop reaction, obtain crude product.
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, quality
Than for 2:8:3.
（2）Alkali cleaning is neutralized
Removing catalyst is separated by filtration, 20% NaHCO is slowly added to in the crude product of reactor3, in the case where temperature is for 95 DEG C,
Stirred with the speed of 160rad/min when adding, when the acid number of crude product is less than 5mgKOH/g, stop adding, continue to stir
15min；
The catalyst being separated off is recycled after simple process, records access times.
（3）Stand at low temperature
Above-mentioned product is placed in into environment temperature to stand at 10 DEG C, after standing 35min, water-yielding stratum is separated after layering, remove moisture.
（4）Crude product after eliminating water is added in lightness-removing column, -0.035MPa is decompressed to, tower top temperature is arranged to 103 DEG C,
Light component is sloughed, the methyl alcohol Jing dehydrating and removing impurities Posterior circle in light component to catalytic esterification kettle is recycled；
The packing layer being provided with the lightness-removing column uses polypropylene plastics cascade ring, a diameter of 70mm of cascade ring used,
Top is using backflow in tubulation.
（5）The crude product for sloughing light component is put in weight-removing column, decompression operation is sloughing heavy constituent；Pressure after decompression
For -0.082MPa, the tower top temperature of weight-removing column is controlled to 121 DEG C, and column bottom temperature is controlled to 158 DEG C, and reflux ratio is set to 2.1, receives
Product at collection tower top.
Through the product that said method process is obtained, after testing, product color is stable, and colourity is light color system, colourity difference
Less, main component is NME（The mixture of dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three）, NME's
Purity is 99.93%, wherein, the content of methyl alcohol is 0.008%, and mono-methyl content is 0.021 ‰；
Quality analyses of the Jing to each composition before and after reaction, up to 99.77%, the selectivity of reaction is for the conversion ratio of reaction
99.90%；
The acid number of product is 0.12mgKOH/g；
The moisture of product is 0.027%；
Using after 33 times, activity decrease degree is less than 10% to catalyst, and stable during use, repeat performance is good, is difficult
Poisoning, will not etching apparatus, pollution is not produced to environment.
Table 1 below is the product index stability change situation that embodiment of the present invention 1-5 is obtained.
Table 1：
Unless otherwise stated, the percentage employed in the present invention is percetage by weight, and ratio of the present invention is matter
Amount ratio.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
To modify to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of method of the continuous catalysis for preparing divalent acid ester plasticizer, it is characterised in that comprise the following steps：Continuously urge
Change esterification, alkali cleaning neutralization and de- weight step.
2. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 1, it is characterised in that
The continuous catalysis esterification, including first time catalytic esterification and second catalytic esterification：
A first time catalytic esterifications：The mass ratio of nylon acid, methyl alcohol and aqueous sulfuric acid cerium catalyst is 1:1.3-1.6：0.02-
0.05 weighs each raw material, adds aqueous sulfuric acid cerium catalyst, is heated to 120-145 DEG C, and pressure is 120-201KPa, reacts 1-2
Hour；
Second catalytic esterification of b：Methyl alcohol is continuously added, methyl alcohol intake is the 143- of methyl alcohol addition in first time catalytic esterification
165%, 130-160 DEG C is heated to, keeping temperature is constant, adds titanate ester catalyst, addition to be reactant gross mass
8.2-10.5 ‰, when acid number is reached less than 5mgKOH/g, is cooled to rapidly 65-85 DEG C, stops reaction.
3. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 2, it is characterised in that
The aqueous sulfuric acid cerium catalyst, is made up of, wherein the quality percentage of cerous sulfate cerous sulfate active component and double mesoporous silicon carriers
It is balance of double mesoporous than for 42-50%.
4. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 3, it is characterised in that
In 3-5nm, big mesoporous aperture is in 10-15nm in the described pair of mesoporous silicon little mesoporous aperture.
5. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 2, it is characterised in that
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, tetraethyl titanate,
The mass ratio of metatitanic acid orthocarbonate and tetraisopropyl titanate is 2:5-8:3.
6. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 5, it is characterised in that
The titanate ester catalyst is, the mixture of tetraethyl titanate, metatitanic acid orthocarbonate and tetraisopropyl titanate, tetraethyl titanate,
The optimum quality ratio of metatitanic acid orthocarbonate and tetraisopropyl titanate is 2:6-7:3.
7. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 1, it is characterised in that
Second catalytic esterification, titanate ester catalyst charge is the 9.4-9.8 ‰ of reactant gross mass.
8. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 1, it is characterised in that
The alkali cleaning neutralization, at 85-95 DEG C, with 20% NaHCO3Stir while adding, stir speed (S.S.) is 100-160rad/min,
When the acid number of crude product is less than 0.5-1.0mgKOH/g, stop adding, continue to stir 10-15min.
9. the method for a kind of continuous catalysis for preparing divalent acid ester plasticizer according to claim 1, it is characterised in that
The de- heavy step, the pressure in weight-removing column is -0.085 to -0.02MPa, and tower top temperature is 113-135 DEG C, and column bottom temperature is
150-160 DEG C, reflux ratio is set to 0.7-2.1.
10. a kind of method of continuous catalysis for preparing divalent acid ester plasticizer according to claim 1, its feature exists
In, the product obtained with methods described, purity is 99.82-99.96%, and the content of methyl alcohol is 0.008-0.03%, mono-methyl content
For 0.003-0.021 ‰.
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| CN1327975A (en) * | 2001-06-09 | 2001-12-26 | 肖增钧 | Process for preparing environment protection type high-boiling-point solvent, 'dimethylester of nylon acid', by ordinary-pressure intermittent method |
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| CN1327975A (en) * | 2001-06-09 | 2001-12-26 | 肖增钧 | Process for preparing environment protection type high-boiling-point solvent, 'dimethylester of nylon acid', by ordinary-pressure intermittent method |
| CN101134725A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method and equipment for producing dimethyl adipate by continuous esterification |
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