CN110845448B - Comprehensive utilization method of solvent and byproducts in HFPO preparation by oxygen oxidation method - Google Patents
Comprehensive utilization method of solvent and byproducts in HFPO preparation by oxygen oxidation method Download PDFInfo
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- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
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Abstract
The invention relates to the technical field of fluorine chemical industry, in particular to a comprehensive utilization method of a solvent and a byproduct in HFPO preparation by an oxygen oxidation method. The comprehensive utilization method of the solvent and the byproducts in the HFPO preparation by the oxygen oxidation method comprises the steps of sequentially separating, alcohol washing, rectifying, alkali washing and drying the fluorocarbon solvent to be purified containing the acyl fluoride byproducts generated in the preparation of hexafluoropropylene oxide by the oxygen oxidation method to obtain the fluorocarbon solvent with the purity of more than 99 wt%. The comprehensive utilization method of the solvent and the byproducts in the HFPO preparation by the oxygen oxidation method has simple process route, can obtain important fluorinated reagents in fluorine chemical industry on one hand, can purify fluorocarbon solvents and then continuously use the fluorocarbon solvents in the reaction for preparing hexafluoropropylene oxide on the other hand, and more importantly, the byproducts are converted into stable neutral esters instead of carboxylic acid, so that the comprehensive utilization purpose of all the byproducts can be realized.
Description
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a comprehensive utilization method of a solvent and a byproduct in HFPO preparation by an oxygen oxidation method.
Background
The preparation of hexafluoropropylene oxide (HFPO) by oxygen oxidation is the most common process for preparing hexafluoropropylene oxide by oxidation of hexafluoropropylene in a fluorocarbon solvent with oxygen as an oxidant.
The common solvents used in the oxygen oxidation process for preparing hexafluoropropylene oxide are chlorofluorocarbons (e.g., CFC-113, etc.) and perfluorohydrocarbons or ethers, which also include both perfluorounsaturated hydrocarbons or ethers and saturated hydrocarbons or ethers.
The production process for preparing hexafluoropropylene oxide by an oxygen oxidation method is divided into two modes of batch method and continuous method production, fluorocarbon solvents in the two modes can be recycled after purification treatment, and the common purification method comprises the following steps: ultraviolet irradiation, water washing liquid separation, rectification and the like, a large amount of low-concentration heteropolyacid dissolved with carboxylic acid substances is generated in the water washing process, and the heteropolyacid cannot be reused and can only be incinerated as dangerous waste for disposal; the reaction is very violent in the water washing process, and the generated virulent hydrogen fluoride is released into the gas phase or the atmosphere of the container after being absorbed too soon, so that accidents such as overpressure, rupture of a rupture disk, environmental pollution and the like are easily caused. A large amount of surfactant can be formed by alkali washing after water washing, so that subsequent rectification cannot be performed, but direct rectification after water washing needs to be performed, and the cost is extremely high because the acidity is too high, and the equipment needs to be completely lined with fluorine. In addition, the reaction for preparing hexafluoropropylene oxide by the oxygen oxidation method is an oxidation reaction, and an intermediate generated in the reaction process is unstable and can continuously react with oxygen and hexafluoropropylene to generate a byproduct. Different solvent systems can generate different types of byproducts, the physical properties of the byproducts are far from each other, and the same treatment method cannot be applied to all the systems.
Patent CN109678700A discloses a comprehensive utilization method of HFPO by-products, which can eliminate peroxide in the by-products in the system by ultraviolet irradiation, but cannot obtain high-purity solvent, and the obtained carboxylic acid solution has high acidity and severe corrosion to equipment, while carbonyl fluoride substances belong to highly toxic, strongly oxidizing and strongly corrosive chemicals and have great safety risk. In addition, the patent does not describe the solvent in detail, and only describes the solvent containing fluorine, and practically no peroxide is generated by using the system of perfluoro saturated hydrocarbon and ether.
Aiming at the problems that the process has higher safety risk, the by-product has higher toxicity and acidity, and the process cannot be suitable for systems of perfluorinated saturated hydrocarbons and ethers, the invention provides a simple and mild process, and the process has more obvious safety, environmental protection and economic benefit.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a comprehensive utilization method of a solvent and byproducts in HFPO preparation by an oxygen oxidation method, which has the advantages of simple process route, lower requirements on equipment, mild and controllable reaction and higher safety, on one hand, an important fluorinated reagent in fluorine chemical industry can be obtained, on the other hand, a fluorocarbon solvent can be purified and then continuously used in the reaction for preparing HFPO, and more importantly, the byproducts are converted into stable neutral esters rather than carboxylic acids and can be further applied or converted, so that the comprehensive utilization purpose of all the byproducts is realized.
The comprehensive utilization method of the solvent and the byproducts in the HFPO preparation by the oxygen oxidation method comprises the following steps:
(1) separation: preparing hexafluoropropylene oxide from oxygen and hexafluoropropylene serving as raw materials under the action of a fluorocarbon solvent, and discharging the fluorocarbon solvent after the fluorocarbon solvent is recycled to obtain the fluorocarbon solvent to be purified, which contains acyl fluoride byproducts;
(2) alcohol washing: adding a fluorocarbon solvent to be purified and alcohol into an alcohol washing device according to the volume ratio of 0.5-2: 1, stirring, standing for layering, discharging from the bottom after layering is completed, and sequentially discharging the fluorocarbon solvent and hydrogen fluoride alcohol solution after alcohol washing; extracting hydrogen fluoride in the hydrogen fluoride alcohol solution by adopting an acid-binding reagent, and then distilling and separating to obtain a byproduct of the hydrogen fluoride reagent and alcohol;
(3) and (3) rectification: rectifying the fluorocarbon solvent after alcohol washing, collecting and recovering the fluorocarbon solvent at the top of the tower, and collecting ester substances at the bottom of the tower;
(4) alkali washing: adding the recovered fluorocarbon solvent and alkaline washing liquid into an alkaline washing device according to the volume ratio of 0.5-2: 1, stirring, standing and layering, discharging from the bottom after layering is completed to obtain the fluorocarbon solvent after alkaline washing, and keeping the alkaline washing liquid in the alkaline washing device for continuous use; the alkali washing is carried out at normal temperature and pressure.
(5) And (3) drying: and drying the fluorocarbon solvent subjected to alkali washing by using silica gel, and reducing the water content to be below 50ppm to obtain the fluorocarbon solvent with the purity of more than 99 wt%.
The oxygen oxidation method for preparing HFPO in the step (1) is a conventional method.
The fluorocarbon solvent in the step (1) is of a structural general formula CnF2n+2The perfluoroalkane has a structural general formula CnF2n+2OmThe ether is one or a mixture of more of ethers, wherein n is 3-10, m is more than 0 and less than or equal to n-1, and n and m are integers; the general formula of the structure is CnF2n+2OmThe ethers of (a) do not contain any form of double bond or-O-functional group.
During the reaction, acyl fluoride by-products are gradually accumulated in the fluorocarbon solvent.
Acyl fluoride by-products with one terminal group of-COF-CF2COF or-CF (CF)3) COF with CF as the other terminal group3O-、CF3CF2O-or CF3CF2CF2O-with a main chain of- (CF)2O)k-、-(CF2CF2O)m-or- (CF)3)CF2O)n-one or more compounds of (a), wherein k, m and n are integers from 1 to 5.
In the step (2), the alcohol is one of anhydrous alcohols containing 1-4 carbon atoms, and includes but is not limited to methanol, ethanol, propanol, butanol, isobutanol and ethylene glycol; ethanol is preferred.
In the step (2), the stirring speed is 10-200 r/min, the stirring temperature is 0-40 ℃, and the stirring time is 1-12 h.
The reaction process involved in the step (2) is as follows: R-COF + CH3CH2OH→RCOOCH2CH3+HF。
And (3) in the step (2), the alcohol washing device is made of a plastic lining material, and the temperature of the washing device is controlled by circulating water.
In the step (2), the concentration of the hydrogen fluoride alcohol solution is 5-40 wt%, the impurity content is lower than 1wt%, and the hydrogen fluoride alcohol solution is stored at a low temperature of 0-15 ℃.
In the step (2), the acid-binding reagent is one of triethylamine, pyrrole, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine and tetrabutylammonium bromide; triethylamine is preferred. When triethylamine is used as an acid-binding reagent, a byproduct, namely triethylamine hydrogen trifluoride, is obtained by distillation separation, and the content of impurities after rectification is lower than 1 wt%; and extracting the acid-binding reagent and the hydrogen fluoride alcohol solution according to the volume ratio of 0.01-1: 1.
And (3) distilling and recycling the alcohol in the hydrogen fluoride alcohol solution in the step (2) after being extracted and regenerated by an acid-binding reagent.
In the step (3), the ester substances are-COOR', -CF at one side end group2COOR' or-CF (CF)3) COOR' with the other terminal group being CF3O-、CF3CF2O-or CF3CF2CF2O-with a main chain of- (CF)2O)k-、-(CF2CF2O)m-or- (CF)3)CF2O)n-wherein k, m and n are integers of 1-5, and R' is a hydrocarbyl group of an alcohol.
In the rectification process, the perfluoropolyether impurities containing acyl fluoride end groups are converted into stable neutral ester substances, can be used for chemical and medical intermediates or surfactants, and can also be used for preparing carboxylic acid, polymer monomers or amide products.
The concentration of the alkaline washing liquid in the step (4) is 2-32 wt%, and the alkali is NaOH, KOH or Ca (OH)2One or more of (a).
The alkaline washing liquid can be reused for many times, and is discharged completely after the alkali content is reduced by 2wt% compared with the alkali content when the alkali is added, and the alkali washing liquid is reused after regeneration treatment.
The alkali wash regeneration method comprises standing, liquid separation, distillation, extraction and the like.
And (5) drying at normal temperature and normal pressure by adopting silicic acid gel.
The mechanism of the invention is as follows:
(1) experimental verification, mass spectrum and nuclear magnetic analysis show that the esterified product of the byproduct can be mutually soluble with the fluorocarbon solvent and is neutral, but the alcoholic solution or the hydrogen fluoride alcoholic solution is layered with the fluorocarbon solvent and is positioned at the upper layer. Putting the esterified substance of the byproduct into water, stirring for 24h, finding that the esterified substance layer is still neutral, and the pH value of a water washing layer is 6, which proves that the esterified substance is different from the common esterified substance and can exist stably in water environment. And (3) putting the byproduct ester into alkali, stirring for 24h, and detecting to find that the ester is completely decomposed. When alcohols are adopted for washing, the alcohols have a certain acid binding effect, so that the reaction does not release a large amount of heat, the hydrogen fluoride is completely absorbed by the alcohols, and the acidity of the fluorocarbon solvent phase is controllable.
By means of the characteristics of the fluorocarbon solvent and the byproduct ester, the process can avoid environment and safety risks caused by untimely absorption due to a large amount of generated hydrogen fluoride by utilizing the special reaction phenomenon of the byproduct acyl fluoride and the alcohol;
the acidic substance and the alcohol are separated from the byproduct ester and the fluorocarbon solvent by utilizing the mechanism of layering of the alcohol and the fluorocarbon solvent and mutual solubility of the perfluoroester and the fluorocarbon solvent, so that the equipment cost of a subsequent rectifying device is reduced.
The boiling point of the by-product is obviously improved due to the generation of the ester substance, so that the fluorocarbon solvent and the by-product ester are easier to separate by rectification. The by-product ester can be stored for a long period of time due to its stable characteristics. The binding acid energy of reagents such as triethylamine and the like is stronger than that of alcohols, and the alcohols can be regenerated and used by extraction. The acid-binding reagent and the alcohol substance are separated only by atmospheric distillation without adopting equipment such as a rectifying tower and the like. The amount of the acid-binding reagent added into the alcohols during separation is controlled within 6 wt%, and the alcohol washing effect can not be influenced.
In the reaction of generating the ester substance, the acyl functional group is effectively protected, and the subsequent reaction can be used for producing amide.
Because various substances are effectively separated in the early stage, the whole process flow only generates trace waste alkali, and the method has obvious economic, environmental protection and safety benefits compared with the traditional post-treatment process.
(2) The by-product fluorination reagent generated in the process can be widely used for production in the fields of medicines, pesticides and the like.
The generated ester substances are that one side end group is-COOR', -CF2COOR' or-CF (CF)3) COOR' with the other terminal group being CF3O-、CF3CF2O-or CF3CF2CF2O-with a main chain of- (CF)2O)k-、-(CF2CF2O)m-or- (CF)3)CF2O)n-wherein k, m and n are integers of 1-5, and R' is a hydrocarbyl group of an alcohol substance. The ester substance can be stably maintained for a long time, has no corrosiveness, and can be used for producing fluorine-containing fluid, perfluoroamide or perfluorocarboxylic acid, and the generated perfluoroamide and perfluorocarboxylic acid can be used as a surfactant on one hand, and can be used as a dispersing agent in the emulsion dispersion polymerization of fluorine-containing monomers such as tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and the like to replace toxic non-environment-friendly surfactants such as perfluorooctanoic acid (PFOA) and the like; on the other hand, since a part of the components are similar to those of perfluoropolyether and the molecular weights are all higher than 400, terminal groups can be further fluorinated for use as the perfluoropolyether.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional 'water washing' process, the purification process of 'alcohol washing, rectification, alkali washing and drying' can purify the fluorocarbon solvent to more than 99wt% for recycling, simultaneously avoids using a large amount of plastic lining materials by equipment, and greatly reduces the equipment cost and the waste liquid treatment cost;
(2) the invention can produce triethylamine hydrogen trifluoride or pyridine hydrofluoride and other fluorination reagents as byproducts in the purification process, the impurity content of the fluorination reagents is lower than 1wt percent, and the fluorination reagents are important high-purity fluorochemical intermediates;
(3) the invention converts perfluoropolyether impurities containing acyl fluoride end groups into stable neutral ester which can be used for producing amide, but perfluorocarboxylic acids or perfluorinated surfactants can not form amide, and the process protects acyl functional groups and expands the application prospect. The fluorocarbon solvent can be purified to more than 99wt% purity, and can be recycled to avoid accumulation of byproducts;
(4) the method has the advantages of simple process route, lower requirement on equipment, no generation of highly toxic byproducts, no generation of byproduct heteroacid, mild and controllable reaction and higher safety, and is suitable for intermittent or continuous production process under the system that the solvent is perfluorinated saturated hydrocarbon or ethers.
Drawings
FIG. 1 is a schematic diagram of an alcohol washing/alkaline washing apparatus of an alcohol washing/alkaline washing process;
in the figure: 1. a fluorocarbon solvent inlet pipe; 2. feeding alcohol/alkali wash into the pipe; 3. a non-condensable gas outlet pipe; 4. a circulating water outlet pipe; 5. a hydrogen fluoride alcohol solution storage tank/an alcohol washing liquid storage tank; 6. a fluorocarbon solvent intermediate tank; 7. and circulating water enters the pipe.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto, and modifications of the technical solutions of the present invention by those skilled in the art should be within the scope of the present invention.
Example 1
The comprehensive utilization method of the solvent and the byproducts in the HFPO preparation by the oxygen oxidation method comprises the following steps:
(1) separation: using oxygen as oxidant, using hexafluoropropylene as raw material, adopting oxygen oxidation method to prepare HFPO, using DY-01 as solvent, making batch reaction and 50 kettles, taking out fluorocarbon solvent to be purified containing acyl fluoride by-product, and finding that its by-product is mainly CF3O(CF(CF3)CF2O)2CF2COF and CF3CF2O(CF2CF2O)2CF(CF3) COF, total content 26 wt%.
(2) Alcohol washing: mixing a fluorocarbon solvent to be purified and absolute ethyl alcohol in a volume ratio of 1:1 in a washing device shown in figure 1, starting stirring, introducing circulating water to control the temperature of a washing kettle to be lower than 40 ℃, stirring for 6 hours, then starting standing, after standing for 2 hours, completing liquid separation, and sequentially discharging the fluorocarbon solvent and hydrogen fluoride ethanol solution after alcohol washing;
measuring the content of hydrogen fluoride in the hydrogen fluoride ethanol solution to be about 4.5 wt%, adding triethylamine into the hydrogen fluoride ethanol solution according to the volume ratio of 1:0.09 to completely convert the hydrogen fluoride into triethylamine hydrogen trifluoride, then distilling at normal pressure to recover components at 78 ℃, measuring the purity of the components to be 98 wt%, and continuously washing the components in the fluorocarbon solvent to be purified;
triethylamine trifluoride had a purity of 99wt% and only a small amount of ethanol impurity.
(3) And (3) rectification: the pH value of the fluorocarbon solvent after alcohol washing is 6, the fluorocarbon solvent is fed from the bottom of a rectifying tower by a pump, intermittent rectification is started after the feeding is finished, DY-01 is known as a mixture, the boiling point of the mixture is 80-110 ℃, therefore, components below 80 ℃ in the rectification process are mainly inert gas in the tower, the components directly enter the tower through the top of the tower to be washed and absorbed, and then are discharged to the air, the total amount accounts for about 1wt% of the fluorocarbon solvent, then, recovered fluorocarbon solvent components at 80-110 ℃ are collected from the top of the rectifying tower, the rectification is stopped after the recovery is finished, heavy components are discharged from the tower kettle, and the rectification process lasts for 4 hours;
the recombination is divided into ester substances, which are mainly ester substances, CF3O(CF(CF3)CF2O)2CF2COOCH2CH3And CF3CF2CF2O(CF2CF2O)2CF(CF3)COOCH2CH3The method is used for producing quaternary ammonium salt surfactant to replace PFOA in the field of fluorine-containing high polymer polymerization.
(4) Alkali washing: introducing the recovered fluorocarbon solvent and NaOH alkaline solution with the concentration of 10 wt% into a washing device shown in figure 1 according to the volume ratio of 1:1 for alkaline washing, stirring for 3 hours, standing for 3 hours, and discharging the fluorocarbon solvent subjected to alkaline washing at the lower layer;
the concentration of the alkali wash liquor is almost unchanged, the alkali wash liquor is still stored in the washing device, the next batch of fluorocarbon solvent is continuously washed, after 17 times of washing, the concentration of the alkali wash liquor is reduced by 2wt%, the lower layer of substances are removed by adopting a standing and layering method, and the upper layer of alkali liquor is heated, evaporated and concentrated by 2wt% for recycling.
(5) And (3) drying: and (3) introducing the alkali-washed fluorocarbon solvent into a silica gel dryer for drying, and after drying for 1h, reducing the water content to be below 50ppm to obtain the fluorocarbon solvent with the purity of 99.7 wt% and the pH value of 6.5.
Example 2
(1) Separation: using oxygen as oxidant, using hexafluoropropylene as raw material, adopting oxygen oxidation method to prepare HFPO, using DY-02 as solvent, making batch reaction for 30 kettles, taking out fluorocarbon solvent to be purified containing acyl fluoride by-product, and finding out that its by-product is mainly CF3CF2CF2O(CF2CF2O)2CF(CF3) COF, total content 19% by weight.
(2) Alcohol washing: mixing a fluorocarbon solvent to be purified and absolute ethyl alcohol in a volume ratio of 2:1 in a washing device shown in figure 1, starting stirring, introducing circulating water to control the temperature of a washing kettle to be lower than 40 ℃, stirring for 6 hours, then starting standing, after standing for 2 hours, completing liquid separation, and sequentially discharging the fluorocarbon solvent and hydrogen fluoride ethanol solution after alcohol washing;
determining that the content of hydrogen fluoride in the hydrogen fluoride ethanol solution is about 3.5 wt%, adding triethylamine into the hydrogen fluoride ethanol solution according to the volume ratio of 1:0.07 to convert the triethylamine into triethylamine hydrogen trifluoride, then distilling at normal pressure to recover components at 78 ℃, determining that the purity of the components is 95 wt%, and the doping amount of an acid-binding reagent is lower than 6 wt%, and continuously washing the components in a fluorocarbon solvent to be purified;
triethylamine trifluoride had a purity of 99wt% and only a small amount of ethanol impurity.
(3) And (3) rectification: the pH value of the fluorocarbon solvent after alcohol washing is 5, the fluorocarbon solvent is fed from the bottom of a rectifying tower by a pump, intermittent rectification is started after the feeding is finished, DY-02 is known as a mixture, the boiling point of the mixture is 100-plus-120 ℃, components lower than 100 ℃ in the rectification process possibly contain a certain amount of organic matters, the mixture enters a VOCs treatment system through the tower top, the VOCs is discharged after the VOCs is treated by the VOCs system, the total amount accounts for about 1wt% of the fluorocarbon solvent, then recovered fluorocarbon solvent components at the temperature of 100-plus-120 ℃ are collected from the top of the rectifying tower, the rectification is stopped after the recovery is finished, heavy components are discharged from the tower bottom, and the rectification process;
heavy component is mainly ester substance CF3CF2CF2O(CF2CF2O)2CF(CF3)COOCH2CH3The method is mainly used for producing polyether substances.
(4) Alkali washing: introducing the recovered fluorocarbon solvent and NaOH alkaline solution with the concentration of 5 wt% into a washing device shown in figure 1 according to the volume ratio of 2:1 for alkaline washing, stirring for 3 hours, standing for 3 hours, and discharging the fluorocarbon solvent subjected to alkaline washing at the lower layer;
the concentration of the alkali solution is almost unchanged, the alkali solution is still stored in the washing device, the next batch of fluorocarbon solvent is continuously washed, after 12 times of washing, the concentration of the alkali solution is reduced by 2wt%, a standing and layering method is adopted to remove substances on the lower layer, and the alkali solution on the upper layer is quantitatively mixed with 32wt% of liquid alkali to obtain 5 wt% of alkali solution for continuous use.
(5) And (3) drying: and (3) introducing the alkali-washed fluorocarbon solvent into a silica gel dryer for drying, and after drying for 20min, reducing the water content to be below 50ppm to obtain the fluorocarbon solvent with the purity of 99.5 wt% and the pH value of 6.5.
Example 3
(1) Separation: using oxygen as oxidant, using hexafluoropropylene as raw material, adopting oxygen oxidation method to prepare HFPO, using DY-03 as solvent, making batch reaction for 30 kettles, taking out fluorocarbon solvent to be purified containing acyl fluoride by-product, and finding that its by-product is mainly CF3OCF2CF2OCF(CF3)CF2OCF(CF3) COF, total content 20 wt%.
(2) Alcohol washing: mixing a fluorocarbon solvent to be purified and anhydrous propanol in a volume ratio of 0.5:1 in a washing device shown in figure 1, starting stirring, introducing circulating water to control the temperature of a washing kettle to be lower than 40 ℃, stirring for 5 hours, then starting standing, after standing for 2 hours, completing liquid separation, and sequentially discharging the fluorocarbon solvent and hydrogen fluoride propanol solution after alcohol washing;
measuring the content of hydrogen fluoride in the hydrogen fluoride propanol solution to be about 4 wt%, adding pyridine into the hydrogen fluoride propanol solution according to the volume ratio of 1:0.3 to convert the pyridine into a hydrogen fluoride pyridine complex, then distilling and recovering components at 97.4 ℃ under normal pressure, measuring the purity of the components to be 95 wt%, and continuously washing the components in the fluorocarbon solvent to be purified;
the hydrogen fluoride pyridine complex was 97 wt% pure with only a small amount of propanol impurity.
(3) And (3) rectification: feeding the alcohol-washed fluorocarbon solvent from the bottom of a rectifying tower by using a pump, starting intermittent rectification after the feeding is finished, wherein DY-03 is known as a mixture, the boiling point of the mixture is 80-90 ℃, components lower than 80 ℃ in the rectification process possibly contain a certain amount of organic matters, entering a VOCs treatment system through the top of the tower, emptying the mixture after the VOCs treatment system, the total amount of the components accounts for about 1wt% of the fluorocarbon solvent, collecting recovered fluorocarbon solvent components at 80-90 ℃ from the top of the rectifying tower, stopping rectification after the recovery is finished, discharging heavy components from the bottom of the tower, and continuing the rectification process for 2 hours;
heavy component is mainly ester substance CF3OCF2CF2OCF(CF3)CF2OCF(CF3)COOCH2CH2CH3The method is mainly used for producing the fluorine-containing polymer monomer and is realized by processes of acidification, decarboxylation and the like.
(4) Alkali washing: introducing the recovered fluorocarbon solvent and NaOH alkaline solution with the concentration of 15 wt% into a washing device shown in figure 1 according to the volume ratio of 0.5:1 for alkaline washing, stirring for 2 hours, standing for 2 hours, and discharging the fluorocarbon solvent subjected to alkaline washing at the lower layer;
the concentration of the alkali solution is almost unchanged, the alkali solution is still stored in the washing device, the next batch of fluorocarbon solvent is continuously washed, after 22 times of washing, the concentration of the alkali solution is reduced by 2wt%, a standing and layering method is adopted to remove substances at the lower layer, and the alkali solution at the upper layer is quantitatively mixed with 32wt% of alkali solution to obtain the alkali solution with the concentration of 5 wt% for continuous use.
(5) And (3) drying: and (3) introducing the alkali-washed fluorocarbon solvent into a silica gel dryer for drying, and after drying for 30min, reducing the water content to be below 50ppm to obtain the fluorocarbon solvent with the purity of 99.2 wt% and the pH value of 6.5.
Comparative example 1
The fluorocarbon solvent to be purified containing the by-product of acyl fluoride obtained in example 1 was treated by conventional water washing.
The water is added into the washing device, then the fluorocarbon solvent to be purified is slowly added, the reaction is very violent, a large amount of hydrogen fluoride gas which cannot be absorbed in time is generated, and a large amount of heat is released.
When fluorocarbon solvent accounting for 10% of the total water volume is slowly added, the pressure of the washing device is quickly increased to 1MPa, and the temperature is quickly increased to over 90 ℃ under the working condition that circulating water is fully opened; and (3) stopping adding the fluorocarbon solvent to be purified, maintaining the reaction for 3 hours, and continuing adding the fluorocarbon solvent containing the by-product after the reaction is completely finished until the washing is finished, wherein the total time is 36 hours.
The water-washed liquid was examined and found to have a pH of 1, but a hydrofluoric acid content of only 10 wt% and 5 wt% of perfluorocarboxylic acid-based substances. The concentration of the generated waste acid is too low and far lower than 40wt% required by industrial production, and the perfluorocarboxylic acid has too many impurities and can only be treated as hazardous waste.
The pH value of the fluorocarbon solvent after washing is 1, the fluorocarbon solvent contains a large amount of carboxylic acid substances, in order to obtain the fluorocarbon solvent with the purity of more than 99wt%, a rectifying tower is adopted for separation, and only a plastic lining material can be selected, so that the obtained perfluorocarboxylic acid substances have seriously damaged acyl fluoride groups and cannot be used for producing amide.
Claims (8)
1. A comprehensive utilization method of a solvent and byproducts in HFPO preparation by an oxygen oxidation method is characterized by comprising the following steps:
(1) separation: preparing hexafluoropropylene oxide from oxygen and hexafluoropropylene serving as raw materials under the action of a fluorocarbon solvent, and discharging the fluorocarbon solvent after the fluorocarbon solvent is recycled to obtain the fluorocarbon solvent to be purified, which contains acyl fluoride byproducts;
the fluorocarbon solvent has a structural general formula of CnF2n+2The perfluoroalkane has a structural general formula CnF2n+2OmThe ether is one or a mixture of more of ethers, wherein n is 3-10, m is more than 0 and less than or equal to n-1, and n and m are integers; the general formula of the structure is CnF2n+2OmThe ethers of (a) do not contain any form of double bond or-O-O-functional group; the acyl fluoride by-product is a side end group of-COF, -CF2COF or-CF (CF)3) COF with CF as the other terminal group3O-、CF3CF2O-or CF3CF2CF2O-with a main chain of- (CF)2O)k-、-(CF2CF2O)m-or- (CF)3)CF2O)n-one or more compounds of (a), wherein k, m and n are integers of 1-5;
(2) alcohol washing: adding a fluorocarbon solvent to be purified and alcohol into an alcohol washing device according to the volume ratio of 0.5-2: 1, stirring, standing for layering, discharging from the bottom after layering is completed, and sequentially discharging the fluorocarbon solvent and hydrogen fluoride alcohol solution after alcohol washing; extracting hydrogen fluoride in the hydrogen fluoride alcohol solution by adopting an acid-binding reagent, and then distilling and separating to obtain a byproduct of the hydrogen fluoride reagent and alcohol;
(3) and (3) rectification: rectifying the fluorocarbon solvent after alcohol washing, collecting and recovering the fluorocarbon solvent at the top of the tower, and collecting ester substances at the bottom of the tower;
(4) alkali washing: adding the recovered fluorocarbon solvent and alkaline washing liquid into an alkaline washing device according to the volume ratio of 0.5-2: 1, stirring, standing and layering, discharging from the bottom after layering is completed to obtain the fluorocarbon solvent after alkaline washing, and keeping the alkaline washing liquid in the alkaline washing device for continuous use;
(5) and (3) drying: and drying the fluorocarbon solvent subjected to alkali washing by using silica gel, and reducing the water content to be below 50ppm to obtain the fluorocarbon solvent with the purity of more than 99 wt%.
2. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: the alcohol in the step (2) is one of anhydrous alcohols containing 1-4 carbon atoms.
3. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: in the step (2), the stirring speed is 10-200 r/min, the stirring temperature is 0-40 ℃, and the stirring time is 1-12 h.
4. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: in the step (2), the concentration of the hydrogen fluoride alcohol solution is 5-40 wt%, the impurity content is lower than 1wt%, and the hydrogen fluoride alcohol solution is stored at a low temperature of 0-15 ℃.
5. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: in the step (2), the acid-binding reagent is one of triethylamine, pyrrole, N-diisopropylethylamine, 4-dimethylaminopyridine and triethanolamine; and extracting the acid-binding reagent and the hydrogen fluoride alcohol solution according to the volume ratio of 0.01-1: 1.
6. The method for preparing HFPO by oxygen oxidation according to claim 1The comprehensive utilization method of the agent and the byproducts is characterized in that: in the step (3), the ester substances are-COOR', -CF at one side end group2COOR' or-CF (CF)3) COOR' with the other terminal group being CF3O-、CF3CF2O-or CF3CF2CF2O-, the main chain is- (CF2O)k-、-(CF2CF2O)m-or- (CF)3)CF2O)n-wherein k, m and n are integers of 1-5, and R' is a hydrocarbyl group of an alcohol.
7. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: the concentration of the alkaline washing liquid in the step (4) is 2-32 wt%, and the alkali is NaOH, KOH or Ca (OH)2One or more of (a).
8. The method of claim 1 for comprehensive utilization of solvents and byproducts in the preparation of HFPO by oxygen oxidation, wherein: and (5) drying at normal temperature and normal pressure by adopting silicic acid gel.
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Address after: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd Address before: 256401 Zibo Huantai County, Shandong Province, Tangshan town Dongyue Fluorosilicic Industrial Park Patentee before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |