CN111592647B - Hydrolysis method of fluorine-containing polyether acyl fluoride - Google Patents
Hydrolysis method of fluorine-containing polyether acyl fluoride Download PDFInfo
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Abstract
The invention discloses a hydrolysis method of fluorine-containing polyether acyl fluoride, wherein fluorine-containing polyether acyl fluoride is hydrolyzed or hydrolyzed in calcium salt solution to prepare fluorine-containing polyether carboxylic acid and hydrofluoric acid gas/calcium fluoride, the hydrolysis is carried out by adding fluorine-containing polyether carboxylic acid into fluorine-containing polyether acyl fluoride and then introducing ultrapure water/calcium salt solution for reaction, the fluorine-containing polyether carboxylic acid added into the fluorine-containing polyether acyl fluoride does not contain moisture and hydrofluoric acid, and the content of hydrofluoric acid in the fluorine-containing polyether carboxylic acid prepared by hydrolysis is controlled to be below 1000ppm/500 ppm. The method effectively reduces the using amount of the water phase during hydrolysis by controlling the feeding sequence during hydrolysis, the adjustment of the composition of the water phase during hydrolysis and the like, and hydrofluoric acid generated by hydrolysis reaction is separated out from the water phase due to water solubility and heating and enters a tail gas device, so that the concentration of hydrofluoric acid in a carboxylic acid product can be successfully reduced, hydrofluoric acid/salt for producing hydrofluoric acid is connected in parallel, meanwhile, the generation of waste liquid is successfully reduced, and the production cost is reduced.
Description
Technical Field
The invention relates to a hydrolysis method of fluorine-containing polyether acyl fluoride, in particular to a hydrolysis process of fluorine-containing polyether acyl fluoride in the process of preparing a fluorine-containing polyether surfactant by photo-oxidation of fluorine-containing olefin, belonging to the field of preparation of fluorine-containing surfactants.
Background
In the field of fluorine-containing compounds, perfluorooctanoic acid is widely used in industry and manufacturing industry because of its water and oil resistance. PFOA-related compounds are used as surfactants and surface-treating agents for textiles, paper, coatings and fire fighting foams. In recent years, perfluorooctanoic acid and other fluorine-and polyfluoroalkyl compounds (PFAS) have come under attack as a result of public attention and public debate. The European Union has confirmed that the substance is persistent, bioaccumulating and harmful to humans. The united nations environmental program committee for examination of organic pollutants has recognized that it meets the standards for persistent organic pollutants. The development of a new product for replacing perfluorooctanoic acid salt has very important significance. At present, the prior patents CN105170018A, CN105170017a and the like disclose that hexafluoropropylene is used for photo-oxidation to produce perfluoropolyether-based surfactant, and the product can successfully replace PFOA and salts thereof to be applied to polymerization of PTFE, PVDF and the like. When the process is used for producing the perfluoropolyether carboxylic acid, the perfluoropolyether acyl fluoride is firstly generated, the substance is active, the perfluoropolyether carboxylic acid and HF are generated by violent heat release during hydrolysis, and the HF is also violent heat release when dissolved in water. The HF has strong water solubility, the hydrofluoric acid and the perfluoropolyether acid have strong corrosivity, and the heat release in the hydrolysis process is severe, so that the reaction is difficult to operate, the equipment is greatly damaged, and the hydrofluoric acid content in the product is high, so that the product quality is influenced.
In the traditional production process, the acyl fluoride-containing end group compound is hydrolyzed, and the acyl fluoride-containing end group compound is directly dripped into excessive water phase for carrying out hydrolysis, in the method, the excessive water phase can effectively enhance the heat exchange effect of the liquid phase, but the method easily causes high concentration of hydrofluoric acid in the liquid phase, so that the subsequent treatment of a crude product has strict requirements on equipment and large loss; and hydrofluoric acid in the product is difficult to treat to a lower level in the subsequent process; meanwhile, the content of hydrofluoric acid in the waste liquid generated in each process is in a higher level, and the difficulty of three-waste treatment is increased.
In the prior art, the optimization of the hydrolysis process of acyl compounds is a problem which is difficult to completely solve in industry in recent years. In the traditional process, the ion concentration, the process loss and the like in the crude product cannot be effectively controlled. In the development and search, there are measures for increasing the yield of sulfonyl compounds by adding other substances, but these measures are not applicable to hydrolysis of acyl fluoride. For example, patent CN105037224a discloses a method for reducing loss and increasing yield in an acyl chloride hydrolysis process, which gradually modifies the concentration of sulfuric acid in a water phase in the hydrolysis process to reduce the solubility of hydrogen chloride in water, and the hydrogen chloride is expelled while taking out heat generated at the moment when a sulfonated feed liquid contacts water, so as to effectively control the temperature in the whole hydrolysis kettle to be lower than a specified value, reduce the temperature at the moment of hydrolysis, reduce the decomposition of tosyl chloride, and reduce loss. The method can effectively improve the yield, but cannot effectively reduce the concentration of sulfuric acid in the product, and has the risk of increasing the concentration of hydrochloric acid in the product while using the hydrochloric acid waste liquid for hydrolysis reaction, and the method has poor applicability in acyl fluoride hydrolysis.
Disclosure of Invention
The invention aims to provide a hydrolysis method of fluoropolyether acyl fluoride, which effectively reduces the using amount of a water phase during hydrolysis by controlling the feeding sequence during hydrolysis, the adjustment of the composition of the water phase during hydrolysis and the like, and hydrofluoric acid generated by hydrolysis reaction is separated out from the water phase due to water solubility and heating and enters a tail gas device, so that the concentration of hydrofluoric acid in a carboxylic acid product can be successfully reduced, hydrogen-producing hydrofluoric acid/a salt for producing hydrofluoric acid is connected in parallel, meanwhile, the generation of waste liquid is successfully reduced, and the production cost is reduced.
The invention is realized by the following technical scheme: a method for hydrolyzing fluoropolyether acid fluoride, wherein fluoropolyether acid fluoride is hydrolyzed to obtain fluoropolyether carboxylic acid and hydrofluoric acid gas, and the hydrofluoric acid gas is sent to a tail gas device, wherein the hydrolysis comprises the following steps: adding fluorine-containing polyether carboxylic acid into fluorine-containing polyether acyl fluoride, then introducing ultrapure water to carry out hydrolysis reaction,
the fluorine-containing polyether carboxylic acid added into the fluorine-containing polyether acyl fluoride contains no moisture and hydrofluoric acid, and the content of the hydrofluoric acid in the fluorine-containing polyether carboxylic acid prepared by hydrolysis is controlled to be below 1000 ppm.
The hydrolysis equation of the fluoropolyether acyl fluoride is as follows:
the mass ratio of the fluorine-containing polyether acyl fluoride to the fluorine-containing polyether carboxylic acid added into the fluorine-containing polyether acyl fluoride is 1: (0.05-0.3).
The molar ratio of the fluorine-containing polyether acyl fluoride to the ultrapure water is 1: (1.5-5).
The temperature of the hydrolysis reaction is 0-10 ℃, and the reaction time is 0.5-6 h.
And deionized water is connected into the tail gas device and is used for dissolving hydrofluoric acid.
A method for hydrolyzing fluorine-containing polyether acyl fluoride, wherein the fluorine-containing polyether acyl fluoride is hydrolyzed in a calcium salt solution (or suspension) to prepare fluorine-containing polyether carboxylic acid and calcium fluoride, and the hydrolyzed tail gas is sent to a tail gas device, and the hydrolysis comprises the following steps: adding fluoropolyether carboxylic acid into fluoropolyether acyl fluoride, introducing calcium salt solution for hydrolysis reaction,
the fluoropolyether carboxylic acid added into the fluoropolyether acyl fluoride contains no moisture and hydrofluoric acid, and the content of hydrofluoric acid in the fluoropolyether carboxylic acid prepared by hydrolysis is controlled to be below 500 ppm.
The hydrolysis equation of the fluoropolyether acyl fluoride is as follows:
the mass ratio of the fluorine-containing polyether acyl fluoride to the fluorine-containing polyether carboxylic acid added into the fluorine-containing polyether acyl fluoride is 1: (0.05-0.3).
Mixing ultrapure water and calcium salt to prepare a calcium salt solution, wherein the molar ratio of the fluoropolyether acyl fluoride to the calcium salt is 1: (0.5-1.5), wherein the molar ratio of the fluoropolyether acyl fluoride to the ultrapure water is 1: (1.5-5).
The calcium salt is one or more of calcium sulfate, calcium carbonate, calcium chloride and the like.
The temperature of the hydrolysis reaction is 0-10 ℃, and the reaction time is 0.5-6 h.
And deionized water is connected into the tail gas device and is used for dissolving hydrofluoric acid.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The method is a novel process for hydrolyzing the fluoropolyether acyl fluoride, and under the condition of keeping the original hydrolysis process equipment unchanged, the concentration of hydrofluoric acid in a carboxylic acid crude product is directly and effectively reduced in the hydrolysis process by adjusting the feeding sequence, the composition of a water phase during hydrolysis, a process control method and the like, and meanwhile, hydrofluoric acid/calcium fluoride generated by hydrolysis can be directly sold as a product after recovery and purification, so that the method has the characteristics of improving the product quality and economic benefits.
(2) The method has certain environmental protection value, devices and equipment related in the reaction process are consistent with requirements required by the production of the original hydrolysis process, byproducts in the reaction process can be sold in the commercial industry after being treated, the concentration of hydrofluoric acid in reaction products is obviously reduced, the corrosion and the loss of production equipment in subsequent processes are effectively reduced, the hydrofluoric acid treatment effect of the subsequent processes is improved, meanwhile, the content of hydrofluoric acid in waste liquid generated in each process is in a lower level, the pressure of three-waste treatment is reduced, meanwhile, the hydrolysis process also successfully reduces the consumption of ultrapure water during hydrolysis, reduces the generation of waste liquid and reduces the production cost.
(3) The method can effectively slow down the reaction rate to prevent potential safety hazard caused by larger instantaneous exothermic heat of the reaction, and during actual use, the fluorine-containing polyether carboxylic acid is added into the fluorine-containing polyether acyl fluoride to dilute the concentration of acyl fluoride while controlling the water phase dripping acceleration rate, thereby achieving the purpose of slowing down the reaction rate.
(4) The method adopts a new hydrolysis mode, and adds the fluoropolyether carboxylic acid in advance in the hydrolysis reaction of the fluoropolyether acyl fluoride, so that the concentration of the perfluoropolyether acyl fluoride can be diluted, the heat exchange effect of a liquid phase is enhanced, the adverse effect caused by violent heat release in hydrolysis after the hydrolysis mode is adjusted is reduced, the hydrolysis product hydrofluoric acid has excellent water solubility, the solubility in the fluoropolyether acyl fluoride and the fluoropolyether carboxylic acid is low, and the preparation of the hydrofluoric acid solution is also facilitated.
(5) The invention changes the control mode that the excessive water phase is adopted in the existing hydrolysis procedure to enhance the liquid phase heat exchange effect, can reduce the concentration of hydrofluoric acid in the semi-finished product by changing the hydrolysis mode, saves the water washing step in the original process, can effectively reduce the using amount of ultrapure water, reduces the pressure of three-waste treatment, reduces the cost and reduces the using amount of ultrapure water.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 330) and 200g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 200r/min, gradually cooling to 5 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 81g of ultrapure water into a feeding funnel, adjusting a valve of the feeding funnel, adding the ultrapure water into the reaction bottle at the speed of 10g/min, adjusting the stirring speed to 180r/min and continuously stirring for 180min after the feeding of the ultrapure water is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation is finished, the lower layer material is perfluoropolyether carboxylic acid, the yield is 101%, and the concentration of hydrofluoric acid is 865ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper material is a water phase, and after the partial material and the product in the tail gas absorption bottle are collected, the partial material and the product are rectified, concentrated and the like, and then trace perfluoropolyether acid is returned to the production system to be prepared into a 40% hydrofluoric acid solution, and the solution is transferred to other processes to be used as a raw material.
Example 2:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 280) and 300g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 300r/min, gradually cooling to 5 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 99g of ultrapure water into a feeding funnel, adjusting a valve of the feeding funnel, adding the ultrapure water into the reaction bottle at the speed of 5g/min, adjusting the stirring speed to 250r/min and continuing stirring for 210min after the feeding of the ultrapure water is completed. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 93%, and the hydrofluoric acid concentration was 800ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper material is a water phase, and after the partial material and the product in the tail gas absorption bottle are collected, the partial material and the product are rectified, concentrated and the like, and then trace perfluoropolyether acid is returned to the production system to be prepared into a 40% hydrofluoric acid solution, and the solution is transferred to other processes to be used as a raw material.
Example 3:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 586) and 100g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring rate at 200r/min, gradually cooling to 10 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 154g of ultrapure water into a feeding funnel, adjusting a valve of the feeding funnel, adding the ultrapure water into the reaction bottle at a rate of 15g/min, adjusting the stirring rate to 200r/min and continuously stirring for 240min after the feeding of the ultrapure water is completed. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of the material is transferred to the next device for liquid separation. After the completion of the liquid separation, the lower layer material was perfluoropolyether carboxylic acid, the yield was 105%, and the hydrofluoric acid concentration was 482ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper material is a water phase, and after the partial material and the product in the tail gas absorption bottle are collected, the partial material and the product are rectified, concentrated and the like, and then trace perfluoropolyether acid is returned to the production system to be prepared into a 40% hydrofluoric acid solution, and the solution is transferred to other processes to be used as a raw material.
Example 4:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight of 420) and 150g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 200r/min, gradually cooling to 10 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 128g of ultrapure water into a feeding funnel, adjusting a valve of the feeding funnel, adding the ultrapure water into the reaction bottle at the speed of 15g/min, adjusting the stirring speed to 200r/min and continuously stirring for 180min after the feeding of the ultrapure water is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 101%, and the hydrofluoric acid concentration was 545ppm. Taking out the product and entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external marketing. The upper material is a water phase, and after the partial material and the product in the tail gas absorption bottle are collected, the partial material and the product are rectified, concentrated and the like, and then trace perfluoropolyether acid is returned to the production system to be prepared into a 40% hydrofluoric acid solution, and the solution is transferred to other processes to be used as a raw material.
Example 5:
adding 2000g of perfluoropolyether acyl fluoride (average molecular weight 1013) and 100g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 200r/min, gradually cooling to 10 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 54g of ultrapure water into a feeding funnel, adjusting a valve of the feeding funnel, adding ultrapure water into the reaction bottle at the speed of 10g/min, adjusting the stirring speed to 120r/min and continuing stirring for 180min after the feeding is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 98.3%, and the hydrofluoric acid concentration was 392ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper material is a water phase, and after the partial material and the product in the tail gas absorption bottle are collected, the partial material and the product are rectified, concentrated and the like, and then trace perfluoropolyether acid is returned to the production system to be prepared into a 40% hydrofluoric acid solution, and the solution is transferred to other processes to be used as a raw material.
Example 6:
adding 433g (calcium chloride solution, feeding calcium salt and perfluoropolyether acyl fluoride according to the mol ratio of 0.8 to 1) into a reaction bottle, starting stirring, controlling the stirring speed at 200r/min, gradually cooling to 10 ℃, adding 100g of deionized water into a subsequent tail gas device of the reaction bottle, adding 1500g of perfluoropolyether acyl fluoride (average molecular weight 805) into a feeding funnel, adjusting a valve of the feeding funnel, adding into the reaction bottle at the speed of 15ml/min, adjusting the stirring speed to 250r/min and continuing stirring for 300min after the materials are overflowed. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, calcium fluoride, calcium chloride and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 99.1%, and the hydrofluoric acid concentration was 282ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper layer materials mainly comprise calcium fluoride, calcium chloride and water, the concentration of hydrofluoric acid in the filtered water phase is lower than 50ppm, the hydrofluoric acid contains calcium chloride and a small amount of perfluoropolyether carboxylic acid, and the hydrofluoric acid can be continuously circulated into the system for hydrolysis; and washing, purifying and drying the solid to obtain the calcium fluoride with the purity of 99%, and selling the calcium fluoride to other workshops for use.
Example 7:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 563) and 150g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 200r/min, gradually cooling to 10 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 458g of calcium chloride solution (feeding calcium salt and perfluoropolyether acyl fluoride according to the molar ratio of 0.8 to 1) into a feeding funnel, adjusting a valve of the feeding funnel, adding into the reaction bottle at the speed of 10ml/min, adjusting the stirring speed to 250r/min and continuing stirring for 240min after the feeding is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, calcium fluoride, calcium chloride and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 104%, and the hydrofluoric acid concentration was 131ppm. Taking out the product and entering the next procedure, and processing the product into ammonium per fluoropolyether carboxylate solution for export sales after a unique dechlorination process. The upper layer materials mainly comprise calcium fluoride, excessive calcium chloride and water, the concentration of hydrofluoric acid in the filtered water phase is lower than 50ppm, and the filtered water phase contains a small amount of perfluoropolyether carboxylic acid and calcium chloride and can be continuously circulated into the system for hydrolysis; and washing, purifying and drying the solid to obtain the calcium fluoride with the purity of 99%, and selling the calcium fluoride to other workshops for use.
Example 8:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 380) and 200g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 220r/min, gradually cooling to 5 ℃, adding 100g of deionized water into a tail gas device behind the reaction bottle, adding 447g of calcium chloride solution (calcium salt and perfluoropolyether acyl fluoride are fed into a feeding funnel according to a molar ratio of 0.5. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, calcium fluoride, calcium chloride and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 101%, and the hydrofluoric acid concentration was 240ppm. Taking out the product and entering the next procedure, and processing the product into ammonium per fluoropolyether carboxylate solution for export sales after a unique dechlorination process. The upper layer materials mainly comprise calcium fluoride, a small amount of calcium chloride and water, the concentration of hydrofluoric acid in the filtered water phase is lower than 50ppm, and the filtered water phase contains a small amount of perfluoropolyether carboxylic acid and calcium chloride and can be continuously circulated into the system for hydrolysis; and washing, purifying and drying the solid to obtain the calcium fluoride with the purity of 99%, and selling the calcium fluoride to other workshops for use.
Example 9:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 452) and 160g of perfluoropolyether carboxylic acid into a reaction bottle, starting stirring, controlling the stirring speed at 180r/min, gradually cooling to 5 ℃, adding 100g of deionized water into a tail gas device subsequent to the reaction bottle, adding 601g of calcium sulfate suspension (calcium salt and perfluoropolyether acyl fluoride are fed according to the mol ratio of 1:1) into a feeding funnel, adjusting a valve of the feeding funnel, adding into the reaction bottle at the speed of 10ml/min, adjusting the stirring speed to 350r/min and continuously stirring for 360min after feeding is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, calcium fluoride, calcium sulfate and water, and part of the material is transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 92.5%, and the hydrofluoric acid concentration was 210ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper layer materials mainly comprise calcium sulfate, calcium fluoride and water, the concentration of hydrofluoric acid in the filtered water phase is lower than 50ppm, and the filtered water phase contains a small amount of perfluoropolyether carboxylic acid and calcium sulfate and can be continuously circulated into the system for hydrolysis; and washing, acidifying, purifying and drying the upper-layer solid to obtain calcium fluoride with the purity of 99%, and selling the calcium fluoride to other workshops for use.
Example 10:
adding 1000g of perfluoropolyether acyl fluoride (average molecular weight 652) into a charging funnel (1), building a hydrolysis device, starting stirring, controlling the stirring rate at 240r/min, gradually cooling the air temperature in the device to 10 ℃, adding 100g of deionized water into a subsequent tail gas device of a reaction bottle, and adding 353g of (calcium carbonate suspension, calcium salt and perfluoropolyether acyl fluoride according to the molar ratio of 0.5. Adjusting a valve of the feeding funnel, feeding the materials in the funnel (1) at a speed of 19ml/min and the materials in the funnel (2) at a speed of 10ml/min into the reaction bottle, and after the feeding is finished, adjusting the stirring speed to 350r/min and continuing stirring for 30min. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, calcium fluoride, a small amount of perfluoropolyether calcium carboxylate, a small amount of calcium carbonate and water, and the partial materials are transferred to the next device for liquid separation. After the liquid separation was completed, the lower layer material was perfluoropolyether carboxylic acid, the yield was 84.2%, and the hydrofluoric acid concentration was 495ppm. Taking out the product and then entering the next procedure to process the product into ammonium perfluoropolyether carboxylate solution for external pinning. The upper layer materials mainly comprise calcium fluoride, a small amount of calcium perfluoropolyether carboxylate, a small amount of calcium carbonate and water, the concentration of hydrofluoric acid in the filtered water phase is lower than 50ppm, and the filtered water phase contains a small amount of perfluoropolyether carboxylic acid and can be continuously circulated into the system for hydrolysis; and washing, acidifying, purifying and drying the upper-layer solid to obtain calcium fluoride with the purity of 90%, wherein all the calcium fluoride except the self-use part is sold.
Comparative example 1:
160g of ultrapure water is added into a reaction bottle, stirring is started, the stirring speed is controlled at 300r/min, the temperature is gradually reduced to 0 ℃, 100g of deionized water is added into a subsequent tail gas device of the reaction bottle, 1000g of perfluoropolyether acyl fluoride (average molecular weight 563) is added into a feeding funnel, a valve of the feeding funnel is adjusted, the perfluoropolyether acyl fluoride is dropwise added into the reaction bottle at the speed of 60g/min, and stirring is continued for 120min after the feeding is finished. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation is finished, the lower layer material is perfluoropolyether carboxylic acid, the yield is 102.1%, and the concentration of hydrofluoric acid is about 8300ppm. And (3) the perfluoropolyether carboxylic acid enters the next working procedure, and after the concentration of hydrofluoric acid is reduced to below 50ppm through multiple washing operations, the perfluoropolyether carboxylic acid is processed into the ammonium perfluoropolyether carboxylate solution for external marketing. The material loss during the washing process was about 13%. The upper layer materials mainly comprise water, hydrofluoric acid and a small amount of perfluoropolyether carboxylic acid, and excessive calcium carbonate is added to precipitate the hydrofluoric acid; and washing, purifying and drying the upper-layer solid to obtain the calcium fluoride with the purity of 99 percent, wherein the calcium fluoride is totally sold except the self-use part.
Comparative example 2:
399g of ultrapure water is added into a reaction bottle, stirring is started, the stirring speed is controlled to be 200r/min, the temperature is gradually reduced to 10 ℃, 100g of deionized water is added into a tail gas device behind the reaction bottle, 1000g of perfluoropolyether acyl fluoride (average molecular weight 451) is added into a feeding funnel, a valve of the feeding funnel is adjusted, the perfluoropolyether acyl fluoride is dropwise added into the reaction bottle at the speed of 45g/min, and stirring is continued for 180min after feeding is completed. After the reaction is finished, the product in the flask is a mixture of perfluoropolyether carboxylic acid, hydrofluoric acid and water, and part of materials are transferred to the next device for liquid separation. After the liquid separation is finished, the lower layer material is perfluoropolyether carboxylic acid, the yield is 108.6%, and the concentration of hydrofluoric acid is about 6800ppm. And (3) the perfluoropolyether carboxylic acid enters the next working procedure, and after the concentration of hydrofluoric acid is reduced to below 50ppm through multiple washing operations, the perfluoropolyether carboxylic acid is processed into the ammonium perfluoropolyether carboxylate solution for external marketing. The material loss during the washing process was 28%. The upper layer materials mainly comprise water, hydrofluoric acid and a small amount of perfluoropolyether carboxylic acid, and excessive calcium carbonate is added to precipitate the hydrofluoric acid; and washing, purifying and drying the upper-layer solid to obtain the calcium fluoride with the purity of 99 percent, wherein the calcium fluoride is totally sold except the self-use part.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications and equivalent variations of the above embodiment according to the technical spirit of the present invention are within the scope of the present invention.
Claims (4)
1. A method for hydrolyzing fluorine-containing polyether acyl fluoride is characterized in that: after adding fluoropolyether carboxylic acid into fluoropolyether acyl fluoride, then introducing calcium salt solution to make hydrolysis reaction to obtain fluoropolyether carboxylic acid and calcium fluoride, feeding the hydrolysis tail gas into tail gas device,
the fluoropolyether carboxylic acid added into the fluoropolyether acyl fluoride contains no moisture and hydrofluoric acid, and the mass ratio of the fluoropolyether acyl fluoride to the fluoropolyether carboxylic acid added into the fluoropolyether acyl fluoride is 1: (0.05-0.3);
the calcium salt solution is prepared by mixing ultrapure water and calcium salt, and the molar ratio of the fluorine-containing polyether acyl fluoride to the calcium salt is 1: (0.5-1.5), wherein the molar ratio of the fluoropolyether acyl fluoride to the ultrapure water is 1: (1.5-5) of,
the content of hydrofluoric acid in the fluoropolyether carboxylic acid prepared by hydrolysis reaction is controlled below 500 ppm.
2. The method for hydrolyzing fluoropolyether acid fluoride according to claim 1, wherein: the calcium salt is one or a mixture of calcium sulfate, calcium carbonate and calcium chloride.
3. The method for hydrolyzing fluoropolyether acid fluoride according to claim 1, wherein: the temperature of the hydrolysis reaction is 0-10 ℃, and the reaction time is 0.5-6 h.
4. The method for hydrolyzing fluoropolyether acid fluoride according to claim 1, wherein: and deionized water is introduced into the tail gas device.
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Citations (4)
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| JPH11189566A (en) * | 1997-12-26 | 1999-07-13 | Daikin Ind Ltd | Method for producing fluoroalkylcarboxylic acid |
| CN1684934A (en) * | 2002-09-25 | 2005-10-19 | 纳幕尔杜邦公司 | Process for preparing fluorocarboxylic acids |
| CN105037224A (en) * | 2015-05-27 | 2015-11-11 | 南通沃兰化工有限公司 | Method for reducing loss and improving yield during acyl chloride hydrolysis process |
| CN105111351A (en) * | 2015-08-12 | 2015-12-02 | 江苏梅兰化工有限公司 | Method for preparing special fluoroether surfactant |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189566A (en) * | 1997-12-26 | 1999-07-13 | Daikin Ind Ltd | Method for producing fluoroalkylcarboxylic acid |
| CN1684934A (en) * | 2002-09-25 | 2005-10-19 | 纳幕尔杜邦公司 | Process for preparing fluorocarboxylic acids |
| CN105037224A (en) * | 2015-05-27 | 2015-11-11 | 南通沃兰化工有限公司 | Method for reducing loss and improving yield during acyl chloride hydrolysis process |
| CN105111351A (en) * | 2015-08-12 | 2015-12-02 | 江苏梅兰化工有限公司 | Method for preparing special fluoroether surfactant |
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