阅读说明：本技术 一种液液传质催化合成叔羧酸的工艺与系统 (Process and system for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer ) 是由 周飞 赖崇伟 蒋乐乐 陶川东 李杰灵 余维新 于 2019-09-25 设计创作，主要内容包括：本发明涉及一种液液传质催化合成叔羧酸的工艺与系统,包括合成单元、催化剂再生单元、反应液处理单元、精制单元。烯烃与酸-羰基金属盐在合成单元液液传质羧基化,而后进入催化剂再生单元,气液传质再生羰基金属盐,再生后进入合成单元使用,独立调控反应液中叔羧酸体积比>20％,从再生单元采出反应液,静止分层再萃取,得到含溶剂的叔羧酸,萃取剂用量约节省2/3,而后经洗涤、中和、精制得到叔羧酸产品。从分层器采出部分酸液作为废酸,新鲜催化剂补入合成单元,废酸量约降低36％。克服了气-液-液传质效果差、羧基化反应和吸羰反应互相影响、烯烃阻碍CO配位、废酸量高、萃取剂用量大、回收能耗高等问题。(The invention relates to a process and a system for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer, which comprises a synthesis unit, a catalyst regeneration unit, a reaction liquid treatment unit and a refining unit. Liquid-liquid mass transfer carboxylation of olefin and acid-carbonyl metal salt in a synthesis unit, then entering a catalyst regeneration unit, gas-liquid mass transfer regeneration of carbonyl metal salt, using in the synthesis unit after regeneration, independently regulating and controlling the volume ratio of tertiary carboxylic acid in reaction liquid to be more than 20%, extracting reaction liquid from the regeneration unit, standing, layering and re-extracting to obtain tertiary carboxylic acid containing solvent, saving about 2/3 of the amount of the extracting agent, and then washing, neutralizing and refining to obtain the tertiary carboxylic acid product. Part of acid liquor is extracted from the delaminator and used as waste acid, and fresh catalyst is supplemented into the synthesis unit, so that the waste acid amount is reduced by about 36%. The problems of poor gas-liquid mass transfer effect, mutual influence of the carboxylation reaction and the carbonyl absorption reaction, blockage of CO coordination by olefin, high waste acid amount, large using amount of an extracting agent, high recovery energy consumption and the like are solved.)

1. a process for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer is characterized by comprising a synthesis unit, a catalyst regeneration unit, a reaction liquid treatment unit and a refining unit;

In the synthesis unit, olefin-containing raw materials are subjected to a carboxylation reaction by acid catalysis and liquid-liquid mass transfer with a carbonyl compound;

In the catalyst regeneration unit, the mixed solution after the reaction of the synthesis unit reacts with CO under the action of an acid catalyst to regenerate the carbonyl compound, the regenerated acid solution containing the carbonyl compound returns to the synthesis unit, and part of the reaction mixed solution is discharged;

In the reaction liquid treatment unit, the discharged mixed liquid of the catalyst regeneration unit is layered into a crude tertiary carboxylic acid product and an acid layer, the acid layer returns to the regeneration unit to discharge a small amount of waste acid, and the waste acid is extracted to obtain the tertiary carboxylic acid and is merged into the crude tertiary carboxylic acid product;

And in the refining unit, refining and purifying the crude tertiary carboxylic acid to obtain a tertiary carboxylic acid product.

2. The liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 1, wherein the acid catalyst is one or more of sulfuric acid, hydrofluoric acid, aqueous boron trifluoride solution and phosphoric acid, or other mixed acids mainly containing the mixture.

3. The liquid-liquid mass transfer catalytic synthesis process of a tertiary carboxylic acid according to claim 1, wherein the carbonyl compound is one or more of a copper-containing carbonyl salt, a cobalt-containing carbonyl salt, a silver-containing carbonyl salt, and an iron-containing carbonyl salt.

4. The liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 1, wherein in the synthesis unit, the molar ratio of the fed acid to the olefin is 15-240, the molar concentration of the carbonyl compound in the acid is 0.2-4.0%, the reaction temperature under a sulfur-and phosphorus-containing acid catalysis system is-3-28 ℃, the reaction temperature under a fluorine-containing acid catalysis system is 35-70 ℃, the reaction pressure is 0.1-5.5 MPa, the reaction time is 0.05-2.5 h, and the volume ratio of the tertiary carboxylic acid in the reaction mixed liquid discharged from the regeneration unit is controlled to be more than 20%.

5. the liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 1, wherein in the catalyst regeneration unit, the regeneration temperature is 0-30 ℃ under a sulfur-and phosphorus-containing acid catalysis system, the regeneration temperature of a fluorine-containing acid catalysis system is 40-75 ℃, the regeneration pressure is 0.5-7.5 MPa, and the regeneration time is 0.2-3.5 h.

6. The liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 1, wherein the reaction liquid treatment unit is configured in such a way that the reaction liquid comes from a catalyst regeneration unit, the reaction liquid is static and layered to obtain acid-containing tertiary carboxylic acid, a small amount of acid liquid is used as waste acid, the rest is returned to the regeneration unit, and the tertiary carboxylic acid is extracted by using an extractant, wherein the dosage of the extractant is 0.05-1 times of the volume of the product tertiary carboxylic acid.

7. The liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 1, wherein the process is a continuous operation or a batch operation.

8. The liquid-liquid mass transfer catalytic synthesis process of a tertiary carboxylic acid according to any one of claims 1 to 7, wherein the olefin-containing feedstock is an olefin having 4 to 16 carbon atoms.

9. The liquid-liquid mass transfer catalytic synthesis process of tertiary carboxylic acid according to claim 8, wherein the olefin-containing feedstock is butene, octene, nonene, or dodecene.

10. a system for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer is characterized by comprising a reaction kettle, a regenerative stirring kettle, a delayer, a first extractor and a second extractor; the reaction kettle is connected with a regeneration stirring kettle, the regeneration stirring kettle comprises a first outlet and a second outlet, the first outlet is a regenerated catalyst outlet which is connected with the reaction kettle through a pipeline with a pump, and the second outlet is a reaction mixed liquid outlet which is connected with a delayer; the acid-containing tertiary carboxylic acid outlet of the delayer is converged with the extraction liquid outlet of the first extractor and is connected with the second extractor, and the lower-layer acid outlet of the second extractor is provided with a pipeline and is connected back to the regeneration stirring kettle.

Technical Field

The invention belongs to the technical field of carboxylic acid preparation, and particularly relates to a process and a system for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer.

Background

the tertiary carboxylic acid and the derivative thereof are important carboxylic acid chemicals, 3 saturated carbon chains are arranged on alpha-carbon connected with carboxyl, the chemical property is stable, the steric hindrance is large, and the acidity, the melting point and the boiling point are all lower than those of the corresponding primary and secondary carboxylic acids. The vinyl versatate is mainly used for producing copolymer latex paint of vinyl versatate and vinyl acetate, has environmental resistance and value which are greatly higher than those of vinyl acetate latex paint, and belongs to high-grade latex paint. The tertiary carboxylate of metals such as cobalt, manganese, lead and the like is a high-efficiency drier for paint and ink, and the tertiary carboxylate of metals such as bismuth, barium, calcium, zirconium and the like can be used for preparing polymers in a catalytic manner. The tertiary carboxylic acid glycidyl ester is a modifier of the high-grade paint, improves the abundance, chemical stability, weather resistance, flexibility and paint film hardness of the finish paint, and reduces VOCs. The tertiary carboxylic acid polyol ester is used for preparing high-grade lubricating oil and has high temperature resistance, rust prevention and shock absorption effects. The tertiary carboxylic acid chloride is used for synthesizing pesticide intermediates and cephalosporin antibiotics.

The main synthetic method of the tertiary carboxylic acid is Koch carbonylation reaction, strong acidic substances such as concentrated sulfuric acid, boron trifluoride, phosphoric acid, hydrofluoric acid, strong acidic ionic liquid, solid acid and the like are used as catalysts, carbonyl absorption metal salts such as copper, silver, iron, nickel, cobalt and the like are used as auxiliary agents to catalyze olefin, CO and water to form the carboxylic acid, the current mainstream production process is BF ₃ hydrate catalyzed Koch reaction, the process condition is mature, the reaction speed is high, the conversion rate is high, the problem is that the reaction pressure is high (more than 5MPa), BF ₃ is decomposed into virulent and highly corrosive HF in the air, and the danger after leakage is extremely high.

Aiming at the mass transfer problem, the existing mass transfer bottleneck needs to be broken, an innovative mass transfer mode is developed, the production efficiency is improved, and the side reaction and the acid consumption (waste acid amount) are reduced. Aiming at the problem of large dosage of the extracting agent, the proportion of the tertiary carboxylic acid in the reaction mixed liquid needs to be independently regulated and controlled, the dosage of the extracting agent is reduced on the premise of not weakening the reaction effect, and the energy consumption for recovery is reduced.

Disclosure of Invention

The invention aims to provide a process for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer, which radically changes the gas-liquid mass transfer mode, improves the production efficiency, and reduces the side reaction and acid consumption (waste acid amount); the proportion of tertiary carboxylic acid in the reaction mixed liquid is independently regulated and controlled, and the problem of large dosage of an extracting agent is solved; the problem that a small amount of olefin is polymerized and reacted in an extraction delayer when the kettle type reactor is back-mixed is solved, the generation of heavy olefin is reduced, and high-energy-consumption impurities such as octadecene which are difficult to separate are avoided. The invention also provides a device system for catalytically synthesizing the tertiary carboxylic acid by liquid-liquid mass transfer.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

A process for catalytically synthesizing tertiary carboxylic acid by liquid-liquid mass transfer comprises a synthesis unit, a catalyst regeneration unit, a reaction liquid treatment unit and a refining unit;

in the synthesis unit, olefin-containing raw materials are subjected to a carboxylation reaction by acid catalysis and liquid-liquid mass transfer with a carbonyl compound;

In the catalyst regeneration unit, the mixed solution after the reaction of the synthesis unit reacts with CO under the action of an acid catalyst to regenerate the carbonyl compound, the regenerated acid solution containing the carbonyl compound returns to the synthesis unit, and the reaction mixed solution is discharged;

In the reaction liquid treatment unit, the discharged mixed liquid of the catalyst regeneration unit is layered into a crude tertiary carboxylic acid product and an acid layer, the acid layer returns to the regeneration unit to discharge a small amount of waste acid, and the waste acid is extracted to obtain the tertiary carboxylic acid and is merged into the crude tertiary carboxylic acid product;

And in the refining unit, refining and purifying the crude tertiary carboxylic acid to obtain a tertiary carboxylic acid product.

In the invention, olefin is an important pi ligand of transition metal, and in the existing method for synthesizing the tertiary carboxylic acid by gas-liquid reaction, the raw material olefin is used as the pi ligand to compete with a CO ligand, so that the generation rate of carbonylation metal is slowed, and the synthesis of the tertiary carboxylic acid is not facilitated. The invention respectively carries out the carboxylation reaction and the carbonyl absorption reaction in different units, thereby avoiding the situation that the raw material olefin obstructs the coordination of CO and carbonylation metal. The two-step reaction can independently select and control the applicable conditions according to respective reaction characteristics, the condition of the union of the two reactions is not needed, the two reactions are not influenced and interfered with each other, and the reaction effect is more favorably improved.

the mixed liquid containing the tertiary carboxylic acid is extracted from the catalyst regeneration unit, so that trace olefin brought out by the synthesis unit due to back mixing is continuously converted into the tertiary carboxylic acid. The existing solution is a batch operation of continuing the reaction for a period of time after the material is fed in, or a continuous operation of transferring the material to another reactor to continue the reaction. The invention can save one carboxylation reactor and is easy to operate continuously, thereby avoiding the polymerization and reaction of the back-mixed olefin and reducing the heavy olefin impurities and the waste acid amount.

Further, the acid catalyst is one or a mixture of sulfuric acid, hydrofluoric acid, boron trifluoride aqueous solution and phosphoric acid or other mixed acid mainly containing the mixture. Preferably 74 to 99 percent of sulfuric acid, 70 to 100 percent of hydrofluoric acid aqueous solution and 65 to 85 percent of boron trifluoride aqueous solution.

Further, the carbonyl compound is one or more of copper-containing carbonyl salt, cobalt-containing carbonyl salt, silver-containing carbonyl salt and iron-containing carbonyl salt, and is preferably carbonyl cuprous salt.

Further, in the synthesis unit, the molar ratio of the fed acid to the alkene is 15-240, the molar concentration of the carbonyl compound in the acid is 0.2-4.0%, the reaction temperature under a sulfur and phosphorus-containing acid catalysis system is-3-28 ℃, preferably 2-18 ℃, the reaction temperature under a fluorine-containing acid catalysis system is 35-70 ℃, preferably 40-55 ℃, the reaction pressure is 0.1-5.5 MPa, preferably 0.4-1.8 MPa, and the reaction time is 0.05-2.5 h, preferably 0.15-0.75 h; the volume proportion of the tertiary carboxylic acid in the discharged reaction mixed liquid is controlled to be more than 20 percent.

The synthesis unit carries out liquid-liquid mass transfer reaction, nonpolar raw material olefin and regenerated polar catalyst liquid (acid liquid of carbonyl compound) enter a carboxylation reaction kettle, and the acid catalyzes the reaction of the olefin and the carbonyl compound to generate the tertiary carboxylic acid. The reaction unit replaces the original gas-liquid mass transfer by a liquid-liquid mass transfer mode, is more beneficial to contact mixing and reaction of reaction materials, improves the production efficiency, and reduces the side reaction and the acid consumption (waste acid amount).

In the prior art method, the proportion of the tertiary carboxylic acid in the reaction mixed liquid changes along with the high and low feeding acid-olefin ratios, the proportion of the tertiary carboxylic acid is not independently regulated and controlled, and in order to increase the reaction effect, feeding with a high acid-olefin ratio leads the volume proportion of the tertiary carboxylic acid to be less than 30 percent, usually less than 15 percent. The invention independently controls the ratio of the fed acid to the olefin and the ratio of the tertiary carboxylic acid in the reaction liquid, so that the ratio of the tertiary carboxylic acid is not influenced by the ratio of the fed acid to the olefin, and the volume ratio of the tertiary carboxylic acid is controlled to be more than 20 percent. The tertiary carboxylic acid with high proportion reduces the density, viscosity and crystallization point of the mixed solution, so that the mixed solution is easier to mix, the mass transfer is increased, the stirring energy consumption is reduced, and the reaction temperature of an industrial device can be reduced to be lower, thereby bringing the advantages of slowing down side reaction, improving the product yield, reducing the acid consumption and the like.

Further, in the catalyst regeneration unit, the regeneration temperature is 0-30 ℃ under a sulfur and phosphorus-containing acid catalysis system, and preferably 5-20 ℃; the regeneration temperature of the fluorine-containing acid catalytic system is 40-75 ℃, and preferably 45-60 ℃; the regeneration pressure is 0.5-7.5 MPa, preferably 0.8-3.5 MPa; the regeneration time is 0.2-3.5 h, preferably 0.35-1.5 h.

Further, the flow of the reaction liquid treatment unit is that the reaction liquid comes from a catalyst regeneration unit, the reaction liquid is static and layered to obtain acid-containing tertiary carboxylic acid, a small amount of acid liquid is used as waste acid, the rest is returned to the regeneration unit, the tertiary carboxylic acid is extracted by using an extracting agent, and the using amount of the extracting agent is 0.05-1 time, preferably 0.2-0.6 time, of the volume of the product tertiary carboxylic acid. According to the liquid-liquid equilibrium principle, the lower the proportion of the tertiary carboxylic acid in the mixed solution is, the more extracting agents are needed for extracting the tertiary carboxylic acid in unit mass, the reaction solution of the tertiary carboxylic acid with high proportion is independently regulated and controlled, so that the acid-containing tertiary carboxylic acid is separated from the acid catalyst phase, the content of the tertiary carboxylic acid in the oil phase after layering is further improved, the using amount of the extracting agent is about 1/3 in the prior art, and the problems of large using amount of the extracting agent and high energy consumption in recovery are solved.

further, the process is a continuous operation or a batch operation.

Further, the olefin-containing raw material is olefin with 4-16 carbon atoms. Butene, octene, nonene, dodecene are preferred.

The invention also comprises a system for catalytically synthesizing the tertiary carboxylic acid by liquid-liquid mass transfer, which comprises a reaction kettle, a regenerative stirring kettle, a delayer, a first extractor and a second extractor; the reaction kettle is connected with a regeneration stirring kettle, the regeneration stirring kettle comprises a first outlet and a second outlet, the first outlet is a regenerated catalyst outlet which is connected with the reaction kettle through a pipeline with a pump, and the second outlet is a reaction mixed liquid outlet which is connected with a delayer; the acid-containing tertiary carboxylic acid outlet of the delayer is converged with the extraction liquid outlet of the first extractor and is connected with a second extractor, and a pipeline is arranged at the lower layer acid outlet of the second extractor and is connected back to the regeneration stirring kettle.

compared with the prior art, the invention has the following beneficial effects:

(1) The carboxylation reaction and the carbonyl absorption reaction are respectively carried out in the synthesis unit and the catalyst regeneration unit, the applicable conditions can be independently selected and controlled according to respective reaction characteristics, the condition of combining the carboxylation reaction and the catalyst regeneration unit is not needed, the two reactions are not influenced and interfered with each other, the problem that the coordination of CO and carbonylation metal is blocked by olefin serving as a raw material is avoided, and the reaction effect is better enhanced;

(2) the synthesis of the tertiary carboxylic acid replaces the existing gas-liquid three-phase mass transfer by a liquid-liquid two-phase mass transfer mode, is more beneficial to the contact mixing and reaction of reaction materials, improves the production efficiency, reduces the side reaction and the acid consumption, and reduces the waste acid amount by about 36 percent;

(3) The tertiary carboxylic acid in the reaction liquid is independently regulated and controlled to ensure that the volume proportion is more than 20 percent, the density, the viscosity and the crystallization point of the mixed liquid are reduced, the mixed liquid is easier to mix, the mass transfer is increased, the stirring energy consumption is reduced, the reaction temperature of an industrial device can be reduced to be lower, and the advantages of slowing down side reaction, improving the product yield, reducing the acid consumption and the like can be brought;

(4) The reaction liquid with high content of tertiary carboxylic acid enables the acid-containing tertiary carboxylic acid and the acid catalyst to be separated in a phase-splitting manner, the tertiary carboxylic acid in the acid-containing tertiary carboxylic acid is extracted, the dosage of the extractant is about 1/3 in the prior art, and the problems of large dosage of the extractant and high energy consumption in recovery are solved;

(5) The mixed liquid containing the tertiary carboxylic acid is immediately extracted from the catalyst regeneration unit, so that trace olefin brought out by the synthesis unit due to back mixing is continuously converted into the tertiary carboxylic acid, one carboxylation reactor is saved, continuous operation is easy, the back mixing olefin is prevented from being polymerized and reacted, and the heavy olefin impurities and the waste acid amount are reduced.

Drawings

FIG. 1 is a schematic view of a process system of the present invention.

Description of reference numerals: 1-a reaction kettle, 2-a regeneration stirring kettle, 3-a layering device, 4-a first extractor and 5-a second extractor.

Detailed Description

The present invention will be described in further detail with reference to examples, which are provided only for illustrating the present invention and are not intended to limit the present invention.

As shown in fig. 1, a system for catalytic synthesis of tertiary carboxylic acid by liquid-liquid mass transfer comprises a reaction kettle 1, a regenerative stirring kettle 2, a delayer 3, a first extractor 4 and a second extractor 5; the reaction kettle 1 is connected with the regeneration stirring kettle 2, the regeneration stirring kettle 2 comprises a first outlet and a second outlet, the first outlet is a regenerated catalyst outlet and is connected with the reaction kettle 1 through a pipeline with a pump, and the second outlet is a reaction mixed liquid outlet and is connected with the delayer 3; the acid-containing tertiary carboxylic acid outlet of the delayer 3 is connected with the regeneration stirring kettle 2 and the first extractor 4 through a pipeline with a pump, and the extract liquid outlet of the first extractor 4 is converged and connected with the second extractor 5.

The synthesis unit is a reaction kettle 1, raw material olefin is continuously added into the synthesis unit, a fresh catalyst is continuously supplemented into the synthesis unit, and the raw material olefin is subjected to acid catalysis and liquid-liquid mass transfer of a carbonyl compound to carry out a carboxylation reaction;

the catalyst regeneration unit is a regeneration stirring kettle 2, the mixed solution after reaction in the synthesis unit reacts with a carboxylation reagent under the action of a catalyst to regenerate the carbonyl compound, the regenerated acid solution containing the carbonyl compound returns to the synthesis unit, and the reaction mixed solution is continuously extracted;

the reaction liquid treatment unit comprises a delayer 3, a first extractor 4 and a second extractor 5, reaction mixed liquid extracted by the catalyst regeneration unit is stood in the delayer 3 and is layered into a crude tertiary carboxylic acid product and an acid layer, part of the acid layer is extracted to the first extractor 4, the rest is returned to the regeneration stirring kettle 2, the tertiary carboxylic acid and the crude tertiary carboxylic acid product extracted by the first extractor 4 are merged into the second extractor 5, the tertiary carboxylic acid containing cyclohexane extractant is extracted at the upper layer, the lower layer acid of the first extractor 4 is discharged to waste acid, and the lower layer acid of the second extractor 5 is returned to the regeneration stirring kettle 2.

The refining unit is used for preparing a tertiary carboxylic acid product by washing, neutralizing and rectifying according to the method in the patent CN 102718646B.

Fresh catalyst acid-metal carbonyl salt solution is prepared for use according to the method in patent CN 100582081.

The reactions of examples 1-5 were carried out using the above system with varying process conditions, and the reaction conditions and results for each example are shown in the following table:

TABLE 1 reaction conditions and results for the different examples

The yield of the tertiary carboxylic acid product is 89-94%, which is 1.08 times that of the prior art, the amount of waste acid is reduced to 84kg/t, which is reduced by 36% compared with the prior art, and the amount of the extractant is about 1/3 in the prior art, so that the problems of large amount of the extractant and high recovery energy consumption are solved, and the method is more environment-friendly.

The above description is only exemplary of the present invention and should not be taken as limiting, and any modifications, equivalents, improvements, etc. that are made within the spirit and the principle of the present invention should be included in the scope of the present invention.