CN108658749B - Concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate - Google Patents
Concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate Download PDFInfo
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Abstract
The invention discloses a concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate, which comprises the following steps: adding fatty alcohol ether carboxylate prepared by an oxidation method and acid into an acidification reactor, and carrying out acidification reaction to generate acid fatty alcohol ether carboxylate to obtain a liquid-phase product; in layering equipment, standing and layering the liquid-phase product obtained in the previous step, and allowing the layered material to enter the next step; separating the standing and layering materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, and concentrating the upper material obtained after separation to obtain a concentrated material; and in solid-liquid separation equipment, carrying out solid-liquid separation on the concentrated material obtained in the last step, recovering the obtained solid-phase material, and taking the obtained primary concentrated product of the liquid-phase material as a product. The invention has the advantages of simple process flow, low operation cost, safe and reliable process, high resource utilization and low energy consumption, and is a clean production process which meets the development requirements of green chemical industry.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate, in particular to a concentration process for preparing fatty alcohol ether carboxylic acid by acidifying fatty alcohol ether carboxylate prepared by an oxidation method, and particularly relates to a method for acidifying and concentrating low-concentration product of fatty alcohol ether carboxylate prepared by a noble metal catalytic oxidation method.
Background
Fatty Alcohol Ether Carboxylate (AEC) series products are novel surfactants with dual properties of anions and non-ions, belong to green surfactants in the three 90 s of the 20 th century, integrate warm naturability, use safety and easy biodegradability into a whole, are currently recognized functional novel products, have very wide application fields, can be used as good detergents, wetting agents, dispersing agents, foaming agents, mild modifiers and the like, and are applied to the industries of cosmetics, families and industrial cleaning, textiles, chemical industry, medicines, energy sources, materials and the like. AEC has good compatibility, can be compatible with any ionic and non-ionic auxiliary agents, particularly has no interference on the conditioning performance of cations, has excellent emulsifying performance on grease and strong anti-ash-change capability.
The technology for preparing the alcohol ether carboxylate by the catalytic oxidation method belongs to a clean production process, has no problem of residual sodium chloroacetate, meets the requirement of clean production, is the key and inevitable direction of future AEC product development, but the product needs further post-treatment.
In the process of preparing AEC by a noble metal catalytic oxidation method, carbon-supported noble metal is adopted as a catalyst, water is used as a solvent for reaction, and alkali is added, so that acid AEC generated by the reaction is reacted to generate salt-type AEC, besides, the concentration of alcohol ether is overlarge, the viscosity of a reaction system is large, the reaction process is not easy to operate, so that the reaction cannot be carried out, different alcohol ethers have different requirements on the reaction concentration, the concentration of the alcohol ether is generally 5-40%, so that the concentration of a reaction product is lower, especially along with the increasing requirements of people on the environmental protection property of the product in recent years, the concentration requirement of the daily chemical industry on a terminal product is also gradually improved, so that a low-concentration surfactant product is inconvenient to use, and the requirements of customers. Therefore, the concentration of the low-concentration product is imperative.
The concentration methods commonly used at present are evaporative concentration and membrane concentration. The MVR evaporation concentration process of the NMMO solvent is reported as patent CN201610389806.3, and comprises a preheating part and an MVR evaporation concentration system, the waste heat of the system is fully utilized through preheating, heat energy does not need to be supplemented additionally, the heat energy consumption is reduced, the MVR evaporation concentration system adopts secondary steam heating, evaporation concentration, secondary steam recompression and an independent vacuum system to realize the concentration purpose. Although the method reduces the heat energy consumption by utilizing the waste heat, the evaporation concentration needs a large amount of energy consumption, high vacuum is needed, the requirement on equipment is high, and the pure evaporation can only improve the concentration and cannot further improve the quality of the concentrated product.
Patent CN201410622171.8 adopts the membrane concentration technology, and the patent is named as "use viscose fiber squeezed liquid to extract the membrane concentration technology of half fine as raw materials", this patent removes large granule impurity through prefiltering earlier with the squeezed alkali lye of viscose fiber production, gets into the microfiltration membrane and handles, and permeate liquid is filtered 2-4 times through the nanofiltration membrane repeatedly, send ceramic membrane filtration after adding water dilution with the concentrate of last time, and the concentrate that obtains adds acid and neutralizes, obtains half fine liquid. This patent filter area is little, and the operating efficiency is low, and concentrated with high costs, is unfavorable for large-scale industrial production.
Disclosure of Invention
The invention aims to provide a concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate, wherein the fatty alcohol ether carboxylate is an AEC product prepared by an oxidation method, the low-concentration AEC product obtained by the oxidation method can be concentrated into a high-concentration product, the concentration requirement of the market on the surfactant is met, the problem of low concentration of the AEC product prepared by the oxidation method is solved, and the problem that part of activated carbon which is difficult to filter and remove is suspended in the product and generates sedimentation after being placed for a long time is solved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect the present invention provides a concentration process for the preparation of a fatty alcohol ether carboxylic acid from a fatty alcohol ether carboxylate comprising the steps of:
first-step acidification: adding fatty alcohol ether carboxylate and acid prepared by an oxidation method into an acidification reactor, wherein the molar ratio of the fatty alcohol ether carboxylate and the acid prepared by the oxidation method is 1 (0.5-10), stirring for 0.5-4 h at the temperature of 20-50 ℃, carrying out an acidification reaction to generate an acid type fatty alcohol ether carboxylate, and directly carrying out next operation on the obtained liquid phase product;
secondly, pressurizing and layering: in layering equipment, keeping the temperature at 75-100 ℃ and the absolute pressure at 0.1-1 MPa, standing and layering the liquid-phase product obtained in the previous step, and enabling the layered material to enter the next step;
the third step is liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
the fourth step is solid-liquid separation: and (3) in solid-liquid separation equipment, operating the temperature to be 20-90 ℃, carrying out solid-liquid separation on the concentrated material obtained in the last step, recovering the obtained solid-phase material, and filling the obtained primary concentrated product of the liquid-phase material as a product or further concentrating the product in the next step.
The concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate further comprises the steps of:
fifthly, adding salt and layering: adding salt into the primary concentrated product of the liquid-phase material obtained in the previous step in an acidification reactor, wherein the adding amount of the salt is 0.1-10% of the mass of the primary concentrated product, stirring at 20-100 ℃ to uniformly mix the system, standing for 0.5-4 h for layering at 75-100 ℃ under the condition that the operating absolute pressure is 0.1-1 MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
the sixth step of liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
seventh step solid-liquid separation: and (3) in solid-liquid separation equipment, performing solid-liquid separation on the upper layer concentrated product phase obtained in the last step at the operation temperature of 20-90 ℃ to obtain a solid phase material and a liquid phase secondary concentrated material, wherein the solid phase material is used in the fifth step, and the liquid phase secondary concentrated material is filled as a product.
The acidification reactor in the first step is at least one of a stirred tank reactor, an electric heating reaction kettle, a steam heating reaction kettle and a stainless steel reaction kettle.
The fatty alcohol ether carboxylate prepared by the oxidation method in the first step is at least one of dodecyl alcohol ether carboxylate, isomeric dodecyl alcohol ether carboxylate and isomeric tridecyl alcohol ether carboxylate, and the mass percentage of solid content is 5-40%.
The acid in the first step or the third step is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid and tartaric acid or an aqueous solution of the acid.
The solid-liquid separation equipment in the fourth step is at least one of sedimentation type solid-liquid separation equipment, filtration type solid-liquid separation equipment, centrifugal type solid-liquid separation equipment and blade type solid-liquid separation equipment.
And in the fifth step, the acidification reactor is at least one of a stirred tank reactor, an electric heating reaction kettle, a steam heating reaction kettle and a stainless steel reaction kettle.
In the fifth step, the salt is at least one of sodium sulfate, sodium chloride, sodium phosphate, potassium sulfate, potassium chloride and potassium phosphate or the water solution of the salt.
The solid-liquid separation equipment in the seventh step is at least one of sedimentation type solid-liquid separation equipment, filtration type solid-liquid separation equipment, centrifugal type solid-liquid separation equipment and blade type solid-liquid separation equipment.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate adopts an acidification and salt addition concentration technology to ensure that the dehydration process is safer and has lower energy consumption. In the concentration process of the low-concentration product, acid is added to acidify the product, and the system is layered by heating, so that the purposes of separating and dehydrating the system are achieved. Compared with distillation dehydration, the dehydration method has good dehydration effect, does not need higher temperature, and has safer process and lower energy consumption.
The concentration process for preparing the fatty alcohol ether carboxylic acid from the fatty alcohol ether carboxylate has good product stability and better quality. The concentrated product is obtained by the coupling technology of acidification concentration, salt addition concentration and filtration impurity removal, and the recovered salt and the recovered active carbon can be directly used as supplementary raw materials in the reaction and concentration processes for recycling, so that the raw materials are saved, the cost is reduced, and the product quality is further improved.
The concentration process for preparing the fatty alcohol ether carboxylic acid from the fatty alcohol ether carboxylate has the advantages of simple process flow, low operation cost, safe and reliable process, high resource utilization, low energy consumption and capability of recycling the catalyst, and is a clean production process which meets the development requirements of green chemical industry.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The equipment used in the embodiment of the invention is as follows: stirred tank reactor, electric heating reaction kettle, steam heating reaction kettle, stainless steel reaction kettle, settling solid-liquid separation equipment, filtering solid-liquid separation equipment, centrifugal solid-liquid separation equipment, acidification reactor, liquid-liquid separation equipment, blade type solid-liquid separation equipment, etc.
Example 1
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1, dissolving alcohol ether in deionized water at a concentration of 20% (80/(320+80) ═ 20%), adding 0.13mol 80g of AEO9 alcohol ether (dodecyl fatty alcohol ether with 9 EO numbers, purchased from Basv China Co., Ltd.) and 320g of deionized water, adding 0.13mol 5.2g of sodium hydroxide, starting stirring at a stirring speed of 100rpm, heating to 80 ℃ to dissolve uniformly, adding 14g of palladium-carbon composite catalyst at 80 ℃ and introducing oxygen and replacing twice, wherein the oxygen is industrial oxygen and has a content of more than 99%, keeping the oxygen pressure of the system at 0.11MPa under a stirring speed of 200rpm, keeping constant oxygen pressure by adopting an intermittent or continuous oxygen feeding mode, starting an oxygen circulating pump to react until the oxygen pressure does not change any more, realizing circulation of the oxygen in the reaction kettle from above the liquid level by adopting the circulating pump, finishing the oxidation reaction for 1.5h, the mass was extruded to form a lauryl alcohol ether carboxylate containing 9 EO numbers.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: adding 500kg of a product obtained by AEO9(BASF alcohol ether code) catalytic oxidation and containing 9 EO-number lauryl alcohol ether carboxylate and 12kg of sulfuric acid with the concentration of 70% into an electric heating reaction kettle, wherein the mass percentage of the solid content of the lauryl alcohol ether carboxylate is 20%, and the molar ratio of the lauryl alcohol ether carboxylate to the sulfuric acid is 1: 0.5, stirring for 2 hours at the temperature of 20 ℃ to perform acidification reaction to generate acid type dodecyl alcohol ether carboxylic acid, and directly performing next operation on the obtained liquid phase product.
(2) Pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 100 ℃, the absolute pressure of the operation is 0.2MPa, the liquid-phase product dodecyl alcohol ether carboxylic acid obtained in the previous step is subjected to standing and layering, the standing is carried out at 100 ℃ for 1h, the layered materials enter the next step, namely two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid solution.
(3) Liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding 12kg of 70% sulfuric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in a settling type solid-liquid separation device at the operation temperature of 50 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the dodecyl alcohol ether carboxylic acid serving as the primary concentrated product of the liquid-phase material reaches 70%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: in a stirred tank reactor, 3kg of anhydrous sodium sulfate is added into the primary concentrated product of the liquid-phase material obtained in the previous step, namely the dodecyl alcohol ether carboxylic acid of the primary concentrated product of the liquid-phase material obtained in the previous step, the salt addition amount is 2 percent of the mass of the primary concentrated product, the stirring is carried out at the temperature of 40 ℃ to ensure that the system is uniformly mixed, the temperature is increased to 90 ℃, the standing is carried out for 1h for layering under the condition that the operation absolute pressure is 0.1MPa, and the layered materials (the upper layer and the lower layer) enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in a settling solid-liquid separation device, wherein the operation temperature is 50 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the dodecyl alcohol ether carboxylic acid in the liquid phase secondary concentrated material reaches 85%, the product yield is 98%, and the dodecyl alcohol ether carboxylic acid can be used as a product for filling.
Example 2
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1.08, the concentration of alcohol ether dissolved in deionized water is 5 percent, 0.065mol of 30g of AEO7 alcohol ether (dodecyl fatty alcohol ether with 7 EO numbers, purchased from Basff China Co., Ltd.) and 570g of deionized water are added, 0.07mol of 2.8g of sodium hydroxide is added, stirring is started, the stirring speed is 200rpm, the temperature is raised to 70 ℃ to ensure that the alcohol ether is dissolved uniformly, adding 90g of platinum-carbon composite catalyst at 70 ℃, introducing oxygen and replacing twice, wherein the oxygen is industrial oxygen with the content of more than 99 percent, under the condition that the stirring speed is 400rpm, the absolute pressure of the oxygen pressure of the system is kept at 0.2MPa, the constant oxygen pressure is kept by adopting an intermittent or continuous oxygen feeding mode, an oxygen circulating pump is started to react until the oxygen pressure is not changed, the circulation of oxygen in the reaction kettle from the position above the liquid level into the liquid is realized by adopting the circulating pump, the oxidation reaction is finished for 2.5h, the material is extruded, and the dodecyl alcohol ether carboxylate containing 7 EO numbers is generated.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in a steam heating reaction kettle, raw materials are AEO7(BASF alcohol ether code), a product obtained by catalytic oxidation contains 500kg of dodecyl alcohol ether carboxylate with 7 EO numbers and 29kg of hydrochloric acid, the mass percentage of solid content of the product is 5%, the molar ratio of the product obtained by catalytic oxidation of AEO7(BASF alcohol ether code) to the hydrochloric acid is 1:5, the mass percentage of the hydrochloric acid is 30%, the mixture is stirred for 1 hour at the temperature of 40 ℃ to generate acidification reaction to generate acid type AEC, and the obtained liquid phase product is directly subjected to the next operation;
(2) pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 90 ℃, the absolute pressure of the operation is 0.3MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out for 3 hours at 90 ℃, the layered materials enter the next step, namely, two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: in liquid-liquid separation equipment, separating the layered materials obtained in the previous step to obtain a lower water phase and an upper material, adding 6kg of 30% hydrochloric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in settling type solid-liquid separation equipment at the operation temperature of 20 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 75%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: adding 1kg of sodium chloride into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirred tank reactor, wherein the salt addition amount is 3% of the mass of the primary concentrated product, stirring at 100 ℃ to uniformly mix the system, standing for 2h for layering at 100 ℃ under the operation absolute pressure of 0.2MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in a settling solid-liquid separation device, wherein the operation temperature is 20 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the dodecyl alcohol ether carboxylic acid in the liquid phase secondary concentrated material reaches 80%, the product yield is 99%, and the dodecyl alcohol ether carboxylic acid can be used as a product for filling.
Example 3
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1, dissolving alcohol ether in deionized water at a concentration of 40% (80/(120+80) ═ 40%), adding 0.13mol 80g XP90 alcohol ether (9 EO number decyl fatty alcohol ether purchased from basf directed company in China) and 120g deionized water, adding 0.13mol 5.2g sodium hydroxide, starting stirring at a stirring speed of 100rpm, heating to 80 ℃ to dissolve uniformly, adding 14g palladium-carbon composite catalyst at 80 ℃ and introducing oxygen and replacing twice, wherein the oxygen is industrial oxygen with a content of 99%, keeping the absolute pressure of the system at 0.11MPa under a stirring speed of 200rpm, keeping constant oxygen pressure by adopting an intermittent or continuous oxygen feeding mode, starting an oxygen circulating pump to react until the oxygen pressure does not change any more, realizing circulation of the oxygen in the reaction kettle from above the liquid level by adopting the circulating pump, finishing the oxidation reaction for 1.5h, the mass was extruded to form a decaalkyl alcohol ether carboxylate containing 9 EO numbers.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in a stainless steel reaction kettle, the raw material is 500kg of product obtained by catalytic oxidation of XP90(BASF alcohol ether code) and 200kg of phosphoric acid, the solid content of the product obtained by catalytic oxidation of XP90(BASF alcohol ether code) is 40% by mass, the molar ratio of the product obtained by catalytic oxidation of XP90(BASF alcohol ether code) to the phosphoric acid is 1:5, the mass percentage of the phosphoric acid aqueous solution is 85% by mass, the product is stirred for 4 hours at the temperature of 20 ℃ to generate acidification reaction to generate acid type AEC, and the liquid phase product is directly subjected to next operation;
(2) pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 80 ℃, the absolute pressure of the operation is 0.5MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out at 80 ℃ for 0.5h, the layered materials enter the next step, namely two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding 40kg of 85% phosphoric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: in a filtering type solid-liquid separation device, the operation temperature is 50 ℃, the concentrated material obtained in the last step is subjected to solid-liquid separation, the obtained solid-phase material active carbon is used for recycling and carrying out catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 73%, the primary concentrated product of the liquid-phase material can be used as a product for filling, and can also be further concentrated in the next step;
(5) adding salt and layering: adding 2kg of potassium sulfate into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirred tank reactor, wherein the salt addition amount is 0.5% of the mass of the primary concentrated product, stirring at 40 ℃ to uniformly mix the system, heating to 90 ℃, standing for 0.5h for layering under the condition that the operation absolute pressure is 0.3MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in a settling solid-liquid separation device, wherein the operation temperature is 50 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the liquid phase secondary concentrated material, namely the decaalkyl alcohol ether carboxylic acid reaches 86%, the product yield is 97%, and the product can be filled as a product.
Example 4
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1, dissolving alcohol ether in deionized water at a concentration of 15% (80/(453+80) ═ 15%), adding 0.13mol 80g XP70 alcohol ether (7 EO number of decyl fatty alcohol ether purchased from Basf Chinese Co., Ltd.) and 453g deionized water, adding 0.13mol 5.2g sodium hydroxide, starting stirring at a stirring speed of 100rpm, heating to 80 ℃ to dissolve uniformly, adding 14g palladium-carbon composite catalyst at 80 ℃ and introducing oxygen twice, wherein the oxygen is industrial oxygen with a content of 99%, keeping the absolute pressure of 0.11MPa at a stirring speed of 200rpm, keeping constant oxygen pressure by adopting an intermittent or continuous oxygen feeding mode, starting an oxygen circulating pump to react until the oxygen pressure does not change any more, realizing circulation of the oxygen in the reaction kettle from above the liquid level by adopting the circulating pump, finishing the oxidation reaction for 1.5h, the mass was extruded to form a decaalkyl alcohol ether carboxylate containing 7 EO numbers.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in an electric heating reaction kettle, the raw material is 500kg and 235kg of citric acid of a product obtained by XP70(BASF alcohol ether code) catalytic oxidation, the product contains 500kg of decyl alcohol ether carboxylate with 7 EO numbers and 235kg of citric acid, the mass percentage content of a solid content of the product obtained by XP70(BASF alcohol ether code) catalytic oxidation is 15%, the molar ratio of the product obtained by XP70(BASF alcohol ether code) catalytic oxidation to the citric acid is 1:8, the mass percentage content of the citric acid is 100%, and the product is stirred for 1.5 hours at the temperature of 40 ℃ to generate acidification reaction to generate acid type AEC, so that a liquid phase product is obtained and directly subjected to the next operation;
(2) pressurizing and layering: in a settling type solid-liquid separation device, the operation temperature is 70 ℃, the absolute pressure of the operation is 1MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out at 85 ℃ for 3.5 hours, the layered materials enter the next step, namely two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: in liquid-liquid separation equipment, separating the layered materials obtained in the previous step to obtain a lower water phase and an upper material, adding 30kg of citric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in settling type solid-liquid separation equipment at the operation temperature of 60 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 75%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: adding 0.25kg of sodium sulfate aqueous solution with the concentration of 40% into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirring tank type reactor, wherein the salt addition amount is 0.1% of the mass of the primary concentrated product, stirring at 40 ℃ to uniformly mix the system, heating to 90 ℃, standing for 1.5h for layering under the condition that the operation absolute pressure is 0.1MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in centrifugal solid-liquid separation equipment, wherein the operation temperature is 70 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the liquid phase secondary concentrated material, namely the decaalkyl alcohol ether carboxylic acid, reaches 85 percent, the product yield is 99 percent, and the product can be filled as a product.
Example 5
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1, the concentration of alcohol ether dissolved in deionized water is 15 percent (80/(453+80) ═ 15 percent), 0.13mol 80g XL90 alcohol ether (isomeric dodecyl alcohol ether with 9 EO numbers, purchased from Basf China Co., Ltd.) and 453g deionized water are added, 0.13mol 5.2g sodium hydroxide is added, stirring is started, the stirring speed is 100rpm, the temperature is raised to 80 ℃ to enable the alcohol ether to be dissolved uniformly, 14g palladium-carbon composite catalyst is added under the condition of 80 ℃, oxygen is introduced and replaced twice, the oxygen is industrial oxygen, the content is more than 99 percent, under the condition of stirring speed of 200rpm, the absolute pressure of the system is kept to be 0.11MPa, the constant oxygen pressure is kept by adopting an intermittent or continuous oxygen feeding mode, an oxygen circulating pump is started to react until the oxygen pressure does not change any more, the circulation of the oxygen in the liquid from the upper part of the liquid surface in a reaction kettle is realized by adopting the circulating pump, the oxidation reaction time is 1.5h, the mass was extruded to form the isomeric decyl alcohol ether carboxylate containing 9 EO numbers.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in an electric heating reaction kettle, raw materials are XL90(BASF alcohol ether code) catalytic oxidation products containing 500kg and 63kg of acetic acid of isomeric dodecyl alcohol ether carboxylate with 9 EO numbers, XL90(BASF alcohol ether code) catalytic oxidation products contain 15% by mass of solid content, XL90(BASF alcohol ether code) catalytic oxidation products and acetic acid have a molar ratio of 1:8, acetic acid mass percent is 100%, the mixture is stirred for 2.5 hours at the temperature of 40 ℃ to generate acidification reaction to generate acid type AEC, and liquid phase products are obtained and directly subjected to next operation;
(2) pressurizing and layering: in a settling type solid-liquid separation device, the operation temperature is 70 ℃, the absolute pressure of the operation is 1MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out at 80 ℃ for 1.5h, the layered materials enter the next step, namely two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding 10kg of acetic acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in settling type solid-liquid separation equipment at the operation temperature of 60 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 72 percent, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: adding 2kg of sodium sulfate and 3kg of potassium sulfate into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirring kettle type reactor, wherein the salt adding amount is 4% of the mass of the primary concentrated product, the sodium sulfate accounts for 40% of the total amount of the sodium sulfate and the potassium sulfate, stirring at 40 ℃ to uniformly mix the system, heating to 90 ℃, standing for 2 hours for layering under the condition that the operation absolute pressure is 0.1MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in centrifugal solid-liquid separation equipment, wherein the operation temperature is 70 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the isomeric dodecyl alcohol ether carboxylic acid in the liquid phase secondary concentrated material reaches 88%, the product yield is 98%, and the product can be filled as a product.
Example 6
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1.1, alcohol ether is dissolved in deionized water with the concentration of 30 percent, 0.21mol of 120g of TO9 alcohol ether (isomeric tridecyl fatty alcohol ether with 9 EO numbers, purchased from Basff Chinese Co., Ltd.) and 280g of deionized water are added, 0.23mol of 9.2g of sodium hydroxide are added, stirring is started with the stirring speed of 300rpm, the temperature is increased TO 90 ℃ TO enable the alcohol ether TO be uniformly dissolved, 18g of palladium-carbon composite catalyst is added under the condition of 90 ℃, oxygen is introduced and replaced twice, the oxygen is industrial oxygen with the content of 99 percent, the system oxygen pressure is kept at 0.2MPa under the condition of stirring speed of 500rpm, an intermittent or continuous oxygen feeding mode is adopted TO keep constant oxygen pressure, a circulating pump is started TO enable the oxygen pressure not TO change any more, the circulating pump is adopted TO realize the circulation of the oxygen in the liquid from above the liquid level in the reaction kettle, the oxidation reaction time is 3 hours, materials are extruded, the isomeric tridecyl alcohol ether carboxylate containing 9 EO numbers is formed.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in an electric heating reaction kettle, raw materials are 500kg of isomeric tridecyl alcohol ether carboxylate containing 9 EO numbers and 49kg of sulfuric acid and 268kg of citric acid which are obtained by catalytic oxidation of TO9(BASF alcohol ether code), the solid content of the product obtained by catalytic oxidation of TO9(BASF alcohol ether code) is 30% by mass, the molar ratio of the product obtained by catalytic oxidation of TO9(BASF alcohol ether code) TO the mixture of citric acid and sulfuric acid is 1:7, the mol percentage of the sulfuric acid is 20% of the total acid mol, the product is stirred for 2 hours at the temperature of 50 ℃ TO generate acidification reaction TO generate acid type AEC, and the obtained liquid phase product is directly subjected TO the next operation;
(2) pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 70 ℃, the absolute pressure of the operation is 0.8MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out for 4 hours at 75 ℃, the layered materials enter the next step, namely, two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding 7kg of 70% sulfuric acid and 40kg of citric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in blade type solid-liquid separation equipment at the operation temperature of 50 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 78%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: adding 7kg of aqueous solution of sodium sulfate, aqueous solution of potassium sulfate and aqueous solution of sodium chloride into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirred tank reactor, wherein the mass fractions of the salts are all 50%, the salt addition amount is 10% of the mass of the primary concentrated product, the sodium sulfate accounts for 33% of the total amount of the sodium sulfate, the potassium sulfate and the sodium chloride, the potassium sulfate accounts for 33% of the total amount of the sodium sulfate, the potassium sulfate and the sodium chloride, stirring the mixture at the temperature of 20 ℃ to uniformly mix the system, heating the mixture to 100 ℃, standing the mixture for 2h for layering under the condition that the operation absolute pressure is 0.7MPa, and allowing the layered materials (an upper layer and a;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in centrifugal solid-liquid separation equipment, wherein the operation temperature is 90 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the isomeric tridecanol ether carboxylic acid of the liquid phase secondary concentrated material reaches 87%, the product yield is 98%, and the isomeric tridecanol ether carboxylic acid can be used as a product for filling.
Example 7
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1.1, alcohol ether is dissolved in deionized water with the concentration of 5 percent, 0.07mol of 40g of TO7 alcohol ether (isomeric tridecyl fatty alcohol ether with 7 EO numbers, purchased from Basff Chinese Co., Ltd.) and 760g of deionized water are added, 0.08mol of 3.1g of sodium hydroxide are added, stirring is started with the stirring speed of 300rpm, the temperature is increased TO 90 ℃ TO enable the alcohol ether TO be uniformly dissolved, 18g of palladium-carbon composite catalyst is added under the condition of 90 ℃, oxygen is introduced and replaced twice, the oxygen is industrial oxygen with the content of 99 percent, the system oxygen pressure is kept at 0.2MPa under the condition of stirring speed of 500rpm, an intermittent or continuous oxygen feeding mode is adopted TO keep constant oxygen pressure, a circulating pump is started TO enable the oxygen pressure not TO change any more, the circulating pump is adopted TO realize the circulation of the oxygen in the liquid from above the liquid level in the reaction kettle, the oxidation reaction time is 3h, the material is extruded, the isomeric tridecyl alcohol ether carboxylate containing 7 EO numbers is formed.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in a steam heating reaction kettle, the raw material is TO7(BASF alcohol ether code), the product obtained by catalytic oxidation of the BASF alcohol ether code contains 500kg of isomeric tridecyl alcohol ether carboxylate with 7 EO numbers and 60kg of hydrochloric acid, the solid content of the product obtained by catalytic oxidation of TO7(BASF alcohol ether code) is 5 percent by mass, and the mol ratio of the product obtained by catalytic oxidation of TO7(BASF alcohol ether code) TO the hydrochloric acid is 1: 10, the mass percentage of the hydrochloric acid is 30%, the mixture is stirred for 1.5 hours at the temperature of 40 ℃ to generate acidification reaction to generate acid type AEC, and a liquid phase product is obtained and directly subjected to the next operation;
(2) pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 90 ℃, the absolute pressure of the operation is 0.1MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out at 90 ℃ for 3.5 hours, the layered materials enter the next step, namely two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: in liquid-liquid separation equipment, separating the layered materials obtained in the previous step to obtain a lower water phase and an upper material, adding 6kg of 30% hydrochloric acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in settling type solid-liquid separation equipment at the operation temperature of 20 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 80%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: in a stirred tank reactor, 1kg of sodium chloride is added into the primary concentrated product of the liquid-phase material obtained in the previous step, the salt addition amount is 3 percent of the mass of the primary concentrated product, the system is uniformly mixed by stirring at the temperature of 75 ℃, the temperature is 80 ℃, the system is kept stand for 4h for layering under the condition that the operation absolute pressure is 0.2MPa, and the layered materials (the upper layer and the lower layer) enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in a settling solid-liquid separation device, wherein the operation temperature is 20 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the isomeric tridecanol ether carboxylic acid of the liquid phase secondary concentrated material reaches 88%, the product yield is 99%, and the isomeric tridecanol ether carboxylic acid can be used as a product for filling.
Example 8
In a 1L high-pressure reaction kettle, according to the molar ratio of the fed alcohol ether to the sodium hydroxide of 1: 1, the concentration of alcohol ether dissolved in deionized water is 15 percent (80/(453+80) ═ 15 percent), 0.13mol 80g XA60 alcohol ether (isomeric dodecyl alcohol ether with 6 EO numbers, purchased from Basf China Co., Ltd.) and 453g deionized water are added, 0.13mol 5.2g sodium hydroxide is added, stirring is started, the stirring speed is 100rpm, the temperature is raised to 80 ℃ to enable the alcohol ether to be dissolved uniformly, 14g palladium carbon composite catalyst is added under the condition of 80 ℃ to introduce oxygen and replace twice, the oxygen is industrial oxygen, the content is more than 99 percent, under the condition of stirring speed of 200rpm, the system oxygen pressure is kept at 0.11MPa, the constant oxygen pressure is kept by adopting an intermittent or continuous oxygen feeding mode, an oxygen circulating pump is started to react until the oxygen pressure does not change any more, the circulation of the oxygen in a reaction kettle from the liquid level to the liquid is realized by adopting the circulating pump, the oxidation reaction time is 1.5h, the mass was extruded to form the isomeric decyl alcohol ether carboxylate containing 6 EO numbers.
A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate prepared by oxidation method, especially the acidification concentration technique of low-concentration product prepared by noble metal catalytic oxidation method, and the separation process for preparing AEC catalyst which can not recover part of active carbon by simple filtration, the method comprises the following steps:
(1) acidifying: in an electric heating reaction kettle, 500kg of isomeric dodecyl alcohol ether carboxylate with 6 EO numbers and 39kg of acetic acid are contained in a product obtained by catalytic oxidation of XA60(BASF alcohol ether code) serving as a raw material, the solid content of the product obtained by catalytic oxidation of XA60(BASF alcohol ether code) is 15% by mass, the molar ratio of the product obtained by catalytic oxidation of XA60(BASF alcohol ether code) to acetic acid is 1:4, the mass percentage of acetic acid is 100%, and the product is stirred for 1.5 hours at the temperature of 40 ℃ to generate an acidification reaction to generate acid type AEC, so that a liquid phase product is obtained and directly subjected to the next operation;
(2) pressurizing and layering: in a settling solid-liquid separation device, the operation temperature is 70 ℃, the absolute pressure of the operation is 1MPa, the liquid-phase product obtained in the previous step is subjected to standing and layering, the standing is carried out at 75 ℃ for 2.5 hours, the layered materials enter the next step, namely, two layers enter the next step simultaneously, the upper layer is alcohol ether carboxylic acid, and the lower layer is acid liquor.
(3) Liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding 12kg of acetic acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
(4) solid-liquid separation was used to remove activated carbon that could not be removed when the catalyst was filtered: performing solid-liquid separation on the concentrated material obtained in the previous step in settling type solid-liquid separation equipment at the operation temperature of 60 ℃, wherein the obtained solid-phase material active carbon is used for recycling and performing catalytic oxidation reaction, the solid content of the obtained primary concentrated product of the liquid-phase material reaches 81%, and the primary concentrated product of the liquid-phase material can be used as a product for filling and can also be further concentrated in the next step;
(5) adding salt and layering: adding 1kg of sodium sulfate and 3kg of potassium sulfate into the primary concentrated product of the liquid-phase material obtained in the previous step in a stirring kettle type reactor, wherein the salt adding amount is 4% of the mass of the primary concentrated product, the sodium sulfate accounts for 25% of the total amount of the sodium sulfate and the potassium sulfate, stirring at 40 ℃ to uniformly mix the system, heating to 95 ℃, standing for 1.5h for layering under the condition that the operation absolute pressure is 1MPa, and allowing the layered materials (the upper layer and the lower layer) to enter the next step;
(6) liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
(7) solid-liquid separation to recover undissolved salts improves final product clarity: and (3) in centrifugal solid-liquid separation equipment, wherein the operation temperature is 70 ℃, solid-liquid separation is carried out on the upper layer concentrated product phase obtained in the last step to obtain a solid phase material and a liquid phase secondary concentrated material, the undissolved salt of the solid phase material is used in the fifth step, the solid content of the isomeric dodecyl alcohol ether carboxylic acid in the liquid phase secondary concentrated material reaches 90%, the product yield is 98%, and the product can be filled as a product.
Comparative example 1
Conventional concentration processes for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates generally:
in a steam heating reaction kettle, 500kg of dodecyl alcohol ether carboxylate containing 7 EO numbers and having a solid content of 30% is added with 25kg of 70% sulfuric acid aqueous solution, and the mixture is stirred for 3 hours at the temperature of 40 ℃ to generate an acidification reaction to generate acid type AEC, so as to obtain a liquid phase product and directly carry out the next operation;
after filtering in a filtering device, heating to 100 ℃, evaporating to remove water, continuously sampling to determine the solid content of the product until the solid content meets the requirement, filtering the product with the composite requirement again, and filling the filtered and concentrated product as the product.
The comparison between the conventional evaporative concentration and the concentration process for preparing fatty alcohol ether carboxylic acid from the fatty alcohol ether carboxylate prepared by the oxidation method of the invention shows that, taking 500kg of raw material, the concentration is from 30% of solid content to 80% of solid content as an example, the fresh industrial steam is used, the process is time-consuming and the salt content of the product is as shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the concentration process for preparing fatty alcohol ether carboxylic acid from the fatty alcohol ether carboxylate prepared by the oxidation method has the advantages of less fresh steam, less energy consumption, shorter whole production process, improved production efficiency and higher product purity, and can bring out salt in the product by dividing water every time, so that the salt content in the product is far lower than that in the traditional method.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate is characterized in that: the method comprises the following steps:
first-step acidification: adding fatty alcohol ether carboxylate and acid prepared by an oxidation method into an acidification reactor, wherein the molar ratio of the fatty alcohol ether carboxylate and the acid prepared by the oxidation method is 1 (0.5-10), stirring for 0.5-4 h at the temperature of 20-50 ℃, carrying out an acidification reaction to generate an acid type fatty alcohol ether carboxylate, and directly carrying out next operation on the obtained liquid phase product;
secondly, pressurizing and layering: in layering equipment, keeping the temperature at 75-100 ℃ and the absolute pressure at 0.1-1 MPa, standing and layering the liquid-phase product obtained in the previous step, and enabling the layered material to enter the next step;
the third step is liquid-liquid separation: separating the layered materials obtained in the previous step in liquid-liquid separation equipment to obtain a lower water phase and an upper material, adding acid into the lower water phase obtained after separation for acidification and reuse, and concentrating the upper material obtained after separation to obtain a concentrated material to enter the next step;
the fourth step is solid-liquid separation: and (3) in solid-liquid separation equipment, operating the temperature to be 20-90 ℃, carrying out solid-liquid separation on the concentrated material obtained in the last step, recovering the obtained solid-phase material, and filling the obtained primary concentrated product of the liquid-phase material as a product or further concentrating the product in the next step.
2. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 1, characterized in that: the concentration process for preparing fatty alcohol ether carboxylic acid from fatty alcohol ether carboxylate further comprises the steps of:
fifthly, adding salt and layering: adding salt into the primary concentrated product of the liquid-phase material obtained in the previous step in an acidification reactor, wherein the adding amount of the salt is 0.1-10% of the mass of the primary concentrated product, stirring at 20-100 ℃ to uniformly mix the system, standing for 0.5-4 h for layering at 75-100 ℃ under the condition that the operating absolute pressure is 0.1-1 MPa, and allowing the layered material to enter the next step;
the sixth step of liquid-liquid separation: separating the layered materials obtained in the previous step in a liquid-liquid separation device to obtain an upper concentrated product phase and a lower high-concentration salt-containing aqueous phase, further treating the lower high-concentration salt-containing aqueous phase to recover salt for the fifth step, and enabling the upper concentrated product to enter the next step;
seventh step solid-liquid separation: and (3) in solid-liquid separation equipment, performing solid-liquid separation on the upper layer concentrated product phase obtained in the last step at the operation temperature of 20-90 ℃ to obtain a solid phase material and a liquid phase secondary concentrated material, wherein the solid phase material is used in the fifth step, and the liquid phase secondary concentrated material is filled as a product.
3. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 1, characterized in that: the acidification reactor in the first step is at least one of a stirred tank reactor, an electric heating reaction kettle, a steam heating reaction kettle and a stainless steel reaction kettle.
4. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 1, characterized in that: the fatty alcohol ether carboxylate prepared by the oxidation method in the first step is at least one of dodecyl alcohol ether carboxylate, isomeric dodecyl alcohol ether carboxylate and isomeric tridecyl alcohol ether carboxylate, and the mass percentage of solid content is 5-40%.
5. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 1, characterized in that: the acid in the first step or the third step is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid and tartaric acid or an aqueous solution of the acid.
6. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 1, characterized in that: the solid-liquid separation equipment in the fourth step is at least one of sedimentation type solid-liquid separation equipment, filtration type solid-liquid separation equipment, centrifugal type solid-liquid separation equipment and blade type solid-liquid separation equipment.
7. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 2, characterized in that: and in the fifth step, the acidification reactor is at least one of a stirred tank reactor, an electric heating reaction kettle, a steam heating reaction kettle and a stainless steel reaction kettle.
8. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 2, characterized in that: in the fifth step, the salt is at least one of sodium sulfate, sodium chloride, sodium phosphate, potassium sulfate, potassium chloride and potassium phosphate or the water solution of the salt.
9. The concentrated process for preparing fatty alcohol ether carboxylic acids from fatty alcohol ether carboxylates according to claim 2, characterized in that: the solid-liquid separation equipment in the seventh step is at least one of sedimentation type solid-liquid separation equipment, filtration type solid-liquid separation equipment, centrifugal type solid-liquid separation equipment and blade type solid-liquid separation equipment.
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| CN108658749A (en) | 2018-10-16 |
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