Method of regenerating surfactants based on fluorinated acids from adsorbent particles saturated with said surfactants

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of regenerating surfactants based on fluorinated acids or their salt from adsorbent particles on which the said surfactants are adsorbed, based on fluorinated acids, involving saturation of adsorbing particles with surfactants based on fluorinated acids or their salt, washing particles of adsorbent on which the surfactant based on fluorinated acid or its salt is adsorbed with water; mixing particles of the adsorbent on which the surfactant based on fluorinated acid or its salt is adsorbed with alcohol or inorganic acid in the presence of water, initiation of etherification of the said surfactant based on fluorinated acid or its salt with the said alcohol to obtain an ether derivative of the said fluorinated surfactant, distillation of the said mixture to obtain a distillate containing the said ether derivative, separation of the said ether derivative from the said distillate and optional return of the remaining distillate to the said mixture and optional conversion of the said ether derivative to the corresponding surfactant based on fluorinated acid or its salt.

EFFECT: efficient method enables use of minimal amount of regenerating liquid and leads to obtaining regenerated particles of adsorbent which can be used repeatedly.

8 cl, 18 ex

 

1. The scope of the invention

The present invention relates to the regeneration of surface-active substances on the basis of fluorinated acids in their acid or salt form with particles of adsorbent saturated specified surfactants on the basis of fluorinated acids or their salts.

2. Background of the invention

Fluorocarbon polymers, i.e. polymers having fluorinated polymer chain, is well known and long used for various purposes due to a number of valuable properties, for example, heat resistance, chemical resistance, resistance to atmospheric conditions, resistance to UV irradiation, etc. Various fluorocarbon polymers are described, for example, in the monograph "Modern Fluoropolymers" (Modern fluoropolymers, edited by John Scheirs, Wiley Science, 1997, These fluoropolymers can be partially fluorinated polymer chain, usually at least fluorinated 40% by weight, or fully fluorinated polymer chain. Examples of fluoropolymers include, in particular, polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene (TFE) and hexaferrite (HFP) (FEP-polymers), performancecriteria (PFA), ethylene-tetrafluorethylene (ETFE) copolymers, trimers tetrafluoroethylene, hexaferrite and fluoride vinylidene (THV) and polymers fluoride vinylidene (PVDF).

A widely used method of producing fluoropolymers include water emulsionstabilizing one or more fluorinated monomers, in the result which is obtained aqueous dispersion of the specified fluoropolymer. Aqueous emulsion polymerization of fluorinated monomers usually involves the use of fluorinated surfactants. Commonly used fluorinated surfactants include performability acids and their salts, in particular, performability ammonium. Other fluorinated surfactants include performaire surfactants described in European patents EP 1059342, EP 712882, EP 752432, EP 816397 and US patents US 6025307 US 6103843 and US 6126849. Other possible surface-active substances are described in U.S. patents№№5229480, 5763552, 5688884, 5700859, 5804650, 5895799, and in the publications WO 00/22002 and WO 00/71590.

Perfluoroine carbonic acid (PFCA) are the preferred emulsifiers for the production of fluorinated polymers, such as polymers such as PTFE, FEP, PFA, perfluorinated elastomers, etc. Especially widely used performability acid (PFOA) in the form of its salts (such as ammonium salt, APFO). However, APFO and other fluorinated surfactants, in particular perfluorinated surface-active substances that are hazardous to the environment. Another important aspect is that such surfactants are expensive the materials, and their losses in the production process should be minimized. So far, these emulsifiers, especially APFO are mandatory, i.e. they do not possess property transfer chain. Therefore, PFOA or APFO, respectively, are a vivid example of an entire class of fluorinated surfactants, in particular, fluorinated surfactants with acidic carboxyl groups.

The fluoropolymers can be used for coating substrates in order to give the latter the desired properties, such as, for example, chemical resistance, resistance to atmospheric conditions, water - and oil-repellent properties, etc. for Example, aqueous dispersions of fluoropolymers can be used to cover kitchen utensils, impregnation of non-woven or woven materials, such as fiberglass, for paper coating or polymer substrates. For economy and ease of dispersion of fluoropolymers typically contain from 35% to 70% weight. fluoropolymer that is usually achieved by use of the concentration process. An alternative for some applications, the fluoropolymers are obtained in the form of granules or powder. To obtain a granulated or powdered fluoropolymers such fluoropolymer usually coagulated, and the resulting coagulate washed with water one or more times to achieve the required level is histoty.

In the production of fluoropolymers in their final commercial form are formed wastewater containing fluorinated surfactant. Such waste water can be obtained when the concentration of the dispersion, purification polymerization reactors and equipment, koagulirovannogo dispersion, and washing the obtained granulated or powdered fluoropolymer. In addition, the waste water containing fluorinated surfactant, may be formed as a result of application of such fluoropolymers. Often, these waste waters contain not only fluorinated surfactant, and other components, for example, a small number of particles of fluoropolymer.

There are several ways to remove perftorirovannyh acids (PFCA) from aqueous media. For example, in the publication WO 02/139593 described method, which uses reverse osmosis. The combined extraction process PFCA from aqueous solutions with low pH value, consisting in the use of chlorinated hydrocarbons and contacting the organic layer with aluminum oxide for regeneration PFCA described in the publications EP 194692 and EP 194691. In the publication DE 2407834 describes the use of silica gel for separation PFCA from aqueous solutions.

Processing water containing PFCA, can be done by using the project for a reverse osmosis followed by adsorption layer of activated carbon and regeneration PFCA z, as described Gasstream and other Plastic masses, 1990), (4), p.75-8 (CIT. by SA 113, 11571). As reported by these Russian authors, water containing PFCA (40-4000 mg PFCA per liter) was purified by reverse osmosis as the initial stage to the PFCA content in less than 20 mg/liter. This content could be further reduced during the first stage of treatment using a layer of activated charcoal. After saturation PFCA saturated activated carbon was subjected to regeneration. Although tested several different methods, the best results were obtained by solvent extraction, in particular a mixture of water, ethyl alcohol, to conventional Soxhlet extractions. But even in this case it was possible to remove only 65% of adsorbed PFCA. Regenerated thus activated carbon showed a decline in activity in the range of 25-40%. Based on these results it is argued that the activated carbon prior to its disposal can only be used 2-3 times.

Usually it is desirable to regenerate fluorinated surfactant from the particles of the adsorbent so that the specified fluorinated surfactant can be reused in the polymerization process, and the particles of the adsorbent can be reused for wastewater treatment. Although the effectiveness of particle hell is orbent may decrease after repeated use, it would be desirable to regenerate the adsorbent particles so that they can be reused more often to the need for their disposal due to unacceptably low levels of efficiency.

Another method of regeneration PFCA of wastewater containing particles of fluoropolymer, includes the use of anion-exchange resin. This method is described in the publications WO 99/62858 and WO 99/62830. According to the publication WO 99/62858 before contacting wastewater with anion-exchange resin from the wastewater are removed particles of fluoropolymer. According to the publication WO 99/62830 before contacting wastewater with ion exchange resin is added to wastewater neinogennye surfactant. Thus, in this way PFCA associated with ion exchange resin according to the mechanism of anion exchange, however, it is believed that the removal process takes place and the physical adsorption on the resin particles. According to the findings of these applications WO specified fluorinated surfactant may be recovered from the anion exchange resin by elution suitable regenerating liquid, removing the specified fluorinated surfactant with anion-exchange resin. The disadvantage of this method of regeneration fluorinated surfactants with anion-exchange resin is that it usually requires the use of greatly the amount of regenerating liquid, that increases the cost and complicates the process of regeneration.

It is therefore desirable to develop another process of regeneration fluorinated surfactants with particles of the adsorbent, so saturated fluorinated surface-active agent. It is desirable that this process was effective, required the use of minimum quantities of regenerating fluid and preferably has led to the regenerated particles of adsorbent that can be repeatedly reused.

3. The invention

The object of the present invention is a method of regeneration of surface-active substances on the basis of fluorinated acids or their salts with adsorbent particles, saturated specified surfactants on the basis of fluorinated acids. This method includes mixing particles of the adsorbent which adsorbed surfactant on the basis of fluorinated acid or a salt thereof, with alcohol and with optional acid. The mixture is usually heated to cause substantial surface-active substances on the basis of fluorinated acid or a salt thereof with an alcohol to obtain an ether derived surfactants based on fluorinated acid. Next, the method involves distillation of this mixture to obtain a distillate containing at asanee ether derivative, the Department indicated broadcasting is derived from the specified distillate and, optionally, return the remaining distillate in this mixture.

The term "surfactant-based fluorinated acid" in the context of the present invention refers to a surfactant having a fluorinated hydrocarbon group and an acid group. For convenience in the following description of the present invention, the term will be used to denote both the acid and salt forms.

The term "particles of the adsorbent in the context of the present invention refers to particles that are able to physically adsorbate specified fluorinated surfactant according to any mechanism of physical adsorption, including, among other things, ionic interaction, causing physical adsorption. Accordingly, the term "particles of the adsorbent includes ion-exchange resin, which is usually associated fluorinated surfactants with ionic groups, in the process of ion exchange, although adsorption on ion-exchange resin may also be the result of a process of physical adsorption, other than a process of ion exchange.

4. Detailed description of the invention

The particles of the adsorbent

Suitable adsorbent particles include carbon black, silica gel, Linyi zeolites. Widely used soot particles. The shape of the absorbent particles is not particularly important. For example, the particles of the adsorbent may have a disc shape may be spherical, cylindrical or sternvitamin. Can also be used a mixture of adsorbent particles having different shapes. The particle size of the adsorbent is usually from 0.05 mm to 20 mm, usually from 0.1 mm to 10 mm, the Practical range of particle sizes is from 0.5 to 5 mm, Adsorbent particles are usually adsorb fluorinated surfactant on its surface, so it is generally preferable to optimize the specific surface of the particles, i.e. the size of the surface in terms of unit weight. Typically, the specific surface of the particles of the adsorbent is from 10 to 5000 m2/g, typically from 100 to 3000 m2/g, but the practical range is from 300 to 2000 m2/year

In addition, as the absorbent particles may be particles of anion exchange resin. Examples of anion exchange resins that can be used for adsorption of fluorinated surfactants in the process of implementation of the present invention include highly, medium and weakly basic anion-exchange resin. The terms hard-, medium -, and weakly basic anion-exchange resin identified in "Encyclopedia of Polymer Science and Engineering" (encyclopedia the eoir and technology of polymers), published by John Wiley & Sons, 1985, volume 8, str, in "Kirk-Othmer", published by John Wiley & Sons, 3rd ed., volume 13, str. As the anion-exchange functional groups are strongly basic anion-exchange resin usually contains a Quaternary ammonium group, mean-resins usually contain tertiary amino groups and weakly basic resins usually contain secondary amines. Examples of commercially available anion exchange resins that can be used in the present invention include AMBERLITE® IRA-402, AMBERJET® 4200, AMBERLITE® IRA-67 and AMBERLITE® IRA-92, manufactured by Rohm & Haas, PUROLITE® A845 (Purolite company GmbH) and LEWATIT® MP-500 (Bayer AG).

It was unexpectedly found that the regeneration process used in the present invention has no adverse effect on the particles of anion exchange resin, and they can be reused for adsorption of surface-active substances on the basis of fluorinated acids from model wastewater.

Adsorbent particles can be in different degrees of saturated surface-active substance on the basis of fluorinated acids, however, as a rule, the process will be more effective at higher levels of saturation of the adsorbing particles. Usually adsorbing particles are saturated surface-active substance on the basis of fluorinated acids on 5-100%, generally at from 30 to 95% of the nominal capacity of the adsorbent particles. Nomi is the real capacity of the adsorbent particles may be determined by saturation "fresh" phase adsorbent 0.1%aqueous solution of surface-active substances on the basis of fluorinated acid to surfactant breakthrough through the adsorbent. Breakthrough is defined as the point at which at least 10% of the amount of fluorinated surfactant contained in the aqueous solution is still present in solution after contact specified aqueous solution with particles of adsorbent.

Saturated absorbent particles may be as a result of various processes of regeneration. For example, saturated absorbent particles may be in the process of removal of surface-active substances on the basis of fluorinated acids from wastewater generated in producing, manufacturing or processing of fluoropolymers. Alternative adsorbent particles can be satisfied by surface-active substances on the basis of fluorinated acids in the process of removing fluorinated surfactants of the dispersions of fluoropolymers as described, for example, in the publication WO 00/35971, or in the process of removing fluorinated surface-active substances from the filtrate after ultrafiltration, as described in U.S. patent 4396266.

Surfactant-based fluorinated acids

The specified surfactant-based fluorinated acid is a fluorinated hydrocarbon surfactant having at least one acid group. Ordinary is this surfactant will be perfluorinated hydrocarbon surface-active substance. Examples of the acid groups are in the specified surfactant include carboxylic acid groups, sulfonic acid groups and phosphoric acid. The method which is the subject of the present invention, particularly suitable for the regeneration of surface-active substances on the basis of (per)fluorinated aliphatic acids or their salts with an adsorbent particles are adsorbed to these surfactants. The method which is the subject of the present invention, can easily be used for regeneration of fluorinated surfactants corresponding to the formula:

where Q represents hydrogen, Cl or F, and Q can be in the end position, and not in end position, Rfrepresents a linear or branched perfluorinated alkylene containing from 4 to 15 carbon atoms, Z represents COO-Marepresents a cation including H+, alkali metal ion or ammonium ion. Representative examples of fluorinated surfactants corresponding to the above formula (I)are performanoe acids and their salts, such as performability acid and its salts, in particular ammonium salt.

Regenerating liquid

In accordance with the object of the present invention, reg is the generation of surface-active substances on the basis of fluorinated acids adsorption of these particles adsorbing particles are mixed with the regenerating liquid, containing alcohol, optional acid and also usually water. Specified regenerating fluid may be prepared in advance and mixed with adsorbent particles, or individual components can be mixed with the above adsorbing particles separately. Although the order of addition is not particularly important, it is generally preferable to add acid as the last component. Adding acid is not required, because the surface-active substance on the basis of fluorinated acids can autocatalytical reaction of esterification with alcohol. However, the acid is usually added to the specified regenerating liquid.

Suitable alcohols which can be used in the present invention include, in particular lower aliphatic alcohols containing 1 to 5 carbon atoms, such as methanol, ethanol and propanol. You can also use aromatic alcohols. Alcohol can also be added in the form of a predecessor of this alcohol. But such predecessor shall form the alcohol under the conditions used to initiate the esterification reaction. Suitable precursors of alcohol can include compounds such as ketals, forming the corresponding alcohols in acidic environment in the specified regeneration fluid or its mixture with adcor youdemi particles. The acid used in the regenerating fluid is preferably an inorganic acid, however, does not exclude the use of organic acids. In addition, the acid is preferably a strong acid, such as, for example, sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid. The number and nature of the acid used is usually selected so that the pH value of the mixture regenerating liquid and adsorbing particles reached not more than 4, preferably not more than 3, and more preferably not more than 2.

The total number of regenerating fluid and its composition is usually determined depending on the subject of regeneration of the saturated particles of adsorbent and the degree of their saturation. Usually regenerating fluid must contain alcohol in stoichiometric quantities or in stoichiometric excess relative to the amount of surface-active substances on the basis of fluorinated acids adsorbed on intended for the regeneration of the adsorbent particles. If these data are not available, it's usually necessary to use a large excess of regenerating fluid. It will not have a negative impact on the regeneration process, however, is a disadvantage because it uses a non-optimal number of regenerating fluid. The specified excess p is generating liquid can be easily discharged from the regenerated adsorbent particles after completion of the regeneration process. The drained liquid can be weighed and analyzed to determine the actual amount and composition of merged regenerating fluid. The composition and quantity of the slit regenerating fluid can then be adjusted by adding appropriate amounts of components to reuse drained regenerating fluid. Reuse regenerating fluid leads to less waste, environmentally harmless and reduces costs.

The volumetric ratio of the regenerating liquid and adsorbing particles preferably equals at least 2, but you can use less volume ratio. However, smaller volume ratio can cause damage to the adsorbing particles due to the voltage generated at lower volume ratios. You can use a higher volume ratio, however, is too large volume ratio is usually uneconomical. Typically, the volume ratio varies between 2 and 4.

The regeneration process

According to a variant implementation of the process which is the subject of the present invention, the mixture of adsorbent particles and regenerating fluid is typically heated to cause etherification surfactants on the basis of fluorinated acid, and the mixture is distilled. In one embodiment, the implementation of infusion is his invention, the heating and distillation can be carried out simultaneously, i.e. the mixture is subjected to distillation immediately after mixing the particles of adsorbent and regenerating fluid. Alternatively, the mixture may be heated for some time, usually up to boiling, followed by distillation. In addition, the esterification reaction can be initiated without heating, for example, by stirring the mixture for some time at room temperature. However, usually it is more efficient to initiate the esterification by heating the mixture.

The regeneration process can be carried out under normal, high low blood pressure. Usually the process is carried out under a pressure from 0.1 to 2 ATM.; convenient to carry out the process under normal pressure, i.e. a pressure of approximately 1 ATM. The mixture is usually heated to the boiling point of the mixture, however, for the conversion of surface-active substances on the basis of fluorinated acids in its ether derivative can be used to lower the temperature. Usually the process is carried out at temperatures from 30 to 100°C., most often from 50 to 85°C.

The mixture containing the particles of adsorbent and the ether derived surfactants based on fluorinated acids, distilled. The resulting distillate contains the specified ether derivative. If the distillate sufficient number of the odes specified ether derivative is usually easily separated from the rest of the distillate in the form of a separate phase. If regenerating fluid contains a sufficient amount of water, the distillate will typically contain a sufficient amount of water. Alternatively, a phase separation can be added to distilled water. Usually specified ether derivative forms the lower phase. Therefore, the specified ether derivative can be easily separated from the distillate, and the remaining distillate may be returned subject to the distillation mixture. Such an embodiment of the present invention makes it easy to regenerate fluorinated surfactant with a minimum quantity of regenerating fluid. In addition, subsequent continuous reuse regenerating liquid distillation can be started directly after mixing regenerating liquid and particulate adsorbent.

It was found that the regeneration process is highly efficient and allows us to reuse the particles of the adsorbent, i.e. they can be regenerated several times before their performance falls below an economically acceptable level, after which they need to dispose of. Further, the present process is characterized by a high removal efficiency of fluorinated surfactants with adsorbent particles, and therefore even when the particles of the adsorbent Podles the tons of recycling because of the loss of efficiency, the residual content of the fluorinated surfactant on the particles of the adsorbent is very low. In addition, other substances, for example, particles of fluoropolymer, which can adsorb on the adsorbent particles in addition to the fluorinated surface-active substances, usually do not interfere with the removal of fluorinated surfactants and regeneration of the particles of the adsorbent. It was found that the regeneration process is able to remove particles of adsorbent significant portion of adsorbed particles of fluoropolymer.

Competent professionals it is clear that after distillation, this process leads to the production of ether-derived surfactants based on fluorinated acids. This ether derivative can be converted into the corresponding surfactant-based fluorinated acids or their salts by hydrolysis of the specified broadcasting derived by the method known to the competent specialists. Thus obtained surface-active substance on the basis of fluorinated acids or their salts have enough high quality, so it can be reused in the preparation of fluoropolymers by the polymerization of fluorinated monomers.

The following examples illustrate in more detail the present izobreteny is, however, the present invention is not limited to the given examples.

EXAMPLES

Examples 1-3

For adsorption on charcoal, served as an adsorbent particles used an aqueous solution of performability ammonium (APFO). Residual free APFO was removed at the stage of regeneration by a single washing with water. The composition of the samples of the aqueous phase was subjected to gravimetric analysis.

In our experiments we used activated charcoal. Activated carbon in granular form with a particle size of 1.5 mm was obtained from Merck.

The regeneration process

The following examples were used following the regeneration process for the adsorption process 120 g (230 ml) powdered activated carbon (wet weight after treatment with water: 277 g) and an aqueous solution of performability ammonium concentration of 25,000 ppm APFO) was stirred at room temperature. Although the mixture looked muddy, after the adsorption process was found only a small number of small particles. Saturated activated carbon once was rinsed with water and transferred into the apparatus for distillation, consisting of a flask, equipped with a mechanical stirrer, thermometer, steam line and the refrigerator. Then added regenerating liquid consisting of methyl alcohol, water and sulfuric acid. The mixture was heated under Proc. of the required pressure prior to the distillation. Condensed pairs were divided into two liquid phases. The lower phase was removed, and the upper phase was returned to the distillation flask. For the first few hours were separated by more than 90% of the lower phase. The distillation was stopped as soon as he ceased to be an increase in the number of lower phase. The lower phase consisted of methyl ester performability acid. And now showed only a negligible number of small particles.

Example 1

During the initial cycle of saturation on charcoal was adsorbirovannoi 34.4 g of APFO. It is 28.6% wt., based on the weight of dry activated carbon. As a result of regeneration was 30.8 g of methyl ester PFOA. This corresponds to the regeneration 89.5% adsorbed APFO.

Example 2

The regenerated activated carbon of example 1 were washed with water (wet weight: 289 g). When the second saturation was adsorbirovannoi 35.5 g of APFO. In the regeneration of activated carbon was 34.5 g of methyl ester PFOA. This corresponds to the regeneration 97.2% adsorbed APFO.

Example 3

Regeneration was carried out essentially according to the previous procedure using regenerated activated carbon of example 2. Was adsorbirovannoi 35.6 g of APFO. As a result of regeneration was obtained 34 g PFOA methyl ester (degree of regeneration 95.5%).

Example 4

Dry active the cell, the coal was loaded into the two glass column (diameter 4.5 cm). The first column contained 201 g, and the second column 205 g of activated charcoal. The volume of each layer was approximately 400 ml Column was connected, and through them was pumped water to remove all gases. Through the column in the upward direction was passed aqueous solution containing 1200 ppm APFO and 30 ppm Genapol™ X080 (nonionic surfactant production company Clariant GmbH), with pH 5.9. The bandwidth was set at the level of a single layer volume per hour. Samples were taken, which was analyzed for residual APFO.

In eluent the first column we have found the following the content of APFO (see table). As expected, in eluent second column APFO were not found.

Adsorbed APFO, gPFOA in affluence
6.6 g<1 ppm
16.6 g4 ppm
22.5 g5 ppm
38.3 g6 ppm
43.5 g7 ppm
46.8 g23 ppm
51.3 g100 ppm
55.6 g 112 ppm

Columns were washed with 5 l of deionized water. The contents of the first column was transferred into a flask and held the above-described regeneration process. As a result of regeneration was 50.6 g of methyl ester PFOA. This corresponds to a recovery of 91% of adsorbed APFO.

Examples 5-18

For adsorption on anion-exchange resins, listed below, used an aqueous solution of performability ammonium (APFO). If you wanted to get fully saturated anion exchange resin, was used surplus APFO relative capacity anion-exchange resin, communicated to her by the manufacturer. Residual free APFO was removed by a single washing with water.

We used the following anion-exchange resin:

A. AMBERLITE™ IRA 402 Cl (produced by the company Rohm & Haas, chloride form) > 1.3 EQ./liter, strongly alkaline

A. AMBERLITE™ IRA 92 (produced by the company Rohm & Haas > 1.6 EQ./liter, slightly alkaline

C. AMBERLYST™ AND 26 HE (the production company Rohm & Haas, hydroxide form) > 0.8 EQ./liter, strongly alkaline

A General description of the process of saturation and regeneration

For the process of saturation moist anion-exchange resin and an aqueous solution of APFO was stirred at room temperature. APFO was added to until the anion-exchange resin is not filled performability acid (PFOA). Saturated anion exchange resin odncrt what about was rinsed with water and transferred into the apparatus for distillation, consisting of a flask, equipped with a mechanical stirrer, thermometer, steam line and the refrigerator. Then added regenerating liquid consisting of methyl alcohol, water and sulfuric acid. The mixture was heated at the required pressure prior to the distillation. Condensed pairs were divided into two liquid phases. The lower phase was removed, and the upper phase was returned to the distillation flask. For the first few hours were separated by more than 90% of the lower phase. The distillation was stopped as soon as he ceased to be an increase in the number of lower phase. The lower phase of the distillate consisted of methyl ester performability acid (IU-PFOA). Anion-exchange resin was separated from the remaining mixture in the flask by filtration or decantation. The liquid can also be used for regeneration of the next portion, for example, after adding the spent methanol and sulfuric acid. After washing the anion-exchange resin with water it can be reused for the next adsorption process.

Examples 5-8

1. The regeneration method of the surface-active substances on the basis of fluorinated acids or their salts with particles of adsorbent on which these adsorbed surfactants on the basis of fluorinated acids, including saturated adder arousih particles surface-active substances on the basis of fluorinated acids or their salts, the washing water particles of the adsorbent which adsorbed surfactant on the basis of fluorinated acid or a salt thereof; mixing the particles of the adsorbent which adsorbed surfactant on the basis of fluorinated acid or a salt thereof, with an alcohol and an inorganic acid in the presence of water, the initiation of the esterification reaction specified surfactants based on fluorinated acid or its salts specified alcohol to ether derivative specified fluorinated surfactants, the distillation of this mixture to obtain a distillate containing the specified ether derivative, the Department specified ether derived from the specified distillate and an optional return the remaining distillate in this mixture, and, optionally, the conversion of the specified ether derivative in the corresponding surfactant-based fluorinated acid or a salt thereof.

2. The method according to claim 1, characterized in that the said adsorbent particles are soot or anion exchange resins.

3. The method according to claim 1, characterized in that the surface-active substance on the basis of fluorinated acids contains perfluorinated aliphatic acid or its salt.

4. The method according to claim 1, characterized in that ukazanniye is an aliphatic alcohol, containing from 1 to 5 carbon atoms.

5. The method according to claim 1, characterized in that the number and nature of the specified acid are selected so that the mixture had a pH value equal to 2 or less.

6. The method according to claim 5, characterized in that the acid is an inorganic acid.

7. The method according to claim 1, characterized in that the specified etherification is initiated by heating the above-mentioned mixture.

8. The method according to claim 1, characterized in that the specified etherification is initiated in the presence of water.



 

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17 cl, 13 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a method for preparation of multivalent carbonyl compounds and to a novel polyvalent carbonyl compound, which may be useful, for example, as intermediate in production of various fluorinated compounds. Polyvalent carbonyl compound is prepared through economically advantageous way from inexpensive substances and with no need of using any complex synthesis stage. In particular, polyvalent alcohol, including alcohols with at least two structures selected from primary, secondary, and tertiary structures, is brought into reaction with acid halide to form polyvalent ester, which is then fluorinated in liquid phase to form perfluorinated polyvalent ester, in which ester bonds, provided by reaction with primary and secondary alcohols, are further cleaved.

EFFECT: expanded synthetic possibilities in organofluoric compound area.

8 cl, 3 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid

FIELD: chemistry.

SUBSTANCE: invention concerns improved method for obtaining (meth)acrylic acid involving steam phase catalytic oxidation of propylene, propane or isobutylene for production of reaction mix, absorption of oxidised reaction product in water to obtain water solution containing (meth)acrylic acid, concentration of water solution in the presence of azeotropic agent and distillation of obtained (meth)acrylic acid in distillation column to obtaining purified (meth)acrylic acid. During operation of distillation column, including operation interruption and resumption, the column is washed with water, and afterwards azeotropic distillation is performed in the presence of azeotropic agent.

EFFECT: efficient and fast cleaning of distillation column with extraction of valuable substance.

5 cl, 5 dwg, 3 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of 2,2-chloro- or dibromophenylacetic acid alkyl ester of the formula (I): wherein X means Cl or Br; n can be a whole number from 1 to 5; R means hydrogen atom, (C1-C8)-alkyl, aryl, heteroaryl, (C1-C8)-alkaoxy, aryloxy group or halogen atom; R1 means (C1-C8)-alkyl. Method involves interaction of 2,2-dichloro- or dibromophenylacetonitrile of the formula (II): wherein X, n and R are given above in 0.8-2 moles of water per 1 mole of nitrile of the formula (II) with 1-8 moles of alcohol of the formula (III): R1OH (III) wherein R1 is given above per 1 mole of nitrile of the formula (II) in the presence of from 1 to 3 moles of HCl or HBr per 1 mole of nitrile of the formula (II) in the presence if necessary of an inert solvent under conditions of this reaction, at reaction temperature from 30 to 60°C. Then method involves heating to temperature 60-100°C and keeping at this temperature. After termination of reaction the reaction mixture is cooled to temperature from 20 to 40°C, diluted with water and the corresponding 2,2-dichloro- or dibromophenylacetic acid alkyl ester of the formula (I) is isolated. Also, invention relates to a method for synthesis of 2,2-dichloro- or dibromophenylacetic acid alkyl ester of the formula (I): wherein X means Cl or Br; n can mean a whole number from 1 to 5; R means hydrogen atom, (C1-C8)-alkyl, aryl, heteroaryl, (C1-C8)-alkoxy, aryl oxy group or halogen atom; R1 means (C1-C8)-alkyl wherein in the first step of synthesis a possibly substituted benzyl cyanide of the formula (IV): wherein n and R are given above is subjected for interaction with chlorine in the presence of the catalytic amount of gaseous hydrogen chloride or with brominating agent to yield the corresponding nitrile of the formula (II): wherein n, X and R are given above, and formed exhausting gas HCl or HBr is used in the second step for conversion of nitrile of the formula (II) to corresponding 2,2-dichloro- or dibromophenylacetic acid alkyl ester of the formula (I). Conversion to the corresponding 2,2-dichloro- or dibromophenylacetic acid alkyl ester of the formula (I) at the second step occurs in 0.8-2 moles of water per 1 mole of nitrile of the formula (II), 1-8 moles of alcohol of the formula (III): R1OH (III) wherein R1 is given above per 1 mole of nitrile of the formula (II) in the presence of HCl or HBr as a gas exhausting from the first step taken in the amount 1-3 moles per 1 mole of nitrile of the formula (II), and if necessary in the presence of a solvent, at the reaction conversion from 30 to 60°C. Then the process involves heating to temperature 60-100°C and keeping at this temperature, and after termination of reaction the reaction mixture is cooled to temperature from 20 to 40°C and diluted with water. Methods provide preparing the end products with high yields and high purity.

EFFECT: improved methods of synthesis.

10 cl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of carboxylic acid esters that are used as components of lacquered resins and components of paint-and varnish materials, especially, as plasticizer for plastics. Method involves interaction of di- or polycarboxylic acids or their anhydrides with alcohols wherein reaction water is removed by azeotropic distillation with alcohol, and liquid removed from reaction by azeotropic distillation is replaced with alcohol completely again. The improvement of periodic method used in synthesis of esters provides enhancing yield of the end product and reducing the reaction process time.

EFFECT: improved method of synthesis.

5 cl, 4 ex

Cleaning method // 2237652
The invention relates to an improved method of purification of the reaction products of the process of direct connection, comprising the reaction of ethylene with acetic acid in the presence of an acid catalyst to obtain ethyl acetate, and cleaning products, recycling, and this cleaning method includes the following stages: (I) feeding the reaction product in column (A) to remove the acid from the base which divert acetic acid, and with its top pick at least a fraction comprising boiling components containing, inter alia, hydrocarbons, ethyl acetate, ethanol, diethyl ether and water, and is directed to the apparatus (A1) for decanting in order to share these top shoulder straps on the phase rich in ethyl acetate, and water (rich in water) phase, (II) a separate return at least part of the rich ethyl acetate phase and almost all of the aqueous phase from the apparatus (A1) for decanting as phlegmy in the upper part of the column (A) or near its top, (III) the filing of the rest of the rich ethyl acetate phase from the apparatus (A1) for decanting in the upper part of the Westfalia refinery unit column (s) or near its top, (IV) the removal from the column (C): and nedogona, including significantly refined ethyl acetate, which is directed to the treatment of the colon is his, acetaldehyde and diethyl ether, which is sent to the column to remove aldehyde, and (C) lateral fraction comprising mainly ethyl acetate, ethanol and some water, which is directed to a point below the point of entry is rich in ethyl acetate phase is removed from the column (A), (V) challenging reset, including acetaldehyde, from the top or near the top of the column for removal of aldehyde and return diethyl ether, isolated from the base of the column to remove aldehyde, etherification reactor and (VI) purification of refined ethyl acetate in column (E)

The invention relates to an improved process for the preparation of butyl acetate by esterification of acetic acid n-butyl alcohol in the presence of an acidic heterogeneous catalyst, separating the resulting reaction water in the form of an azeotrope with azeotropes agent and the selection of the target product, and acetic acid and n-butyl alcohol is fed to the etherification in a molar ratio of 1.00: 1,05, and the process is conducted in two sequential reactors, the first of which is a column type reactor filled with an acidic heterogeneous catalyst, and the second is a reactive distillation reactor, the upper and lower part of which is filled by the nozzle, and the middle part is filled molded cation exchange resin, and in the upper part of the second distillation reactor serves benzene as azeotroping agent

The invention relates to the process of extracting the ethyl acetate from the reaction mixtures
The invention relates to the field of chemistry, and more specifically, to method selection monoisobutyrate-2,2,4-trimethyl-1,3-pentanediol from condensation products of samalanga aldehyde in the presence of a catalyst is an aqueous solution of alkali

The invention relates to chemical technology, and in particular to methods of separation hardly separated commercial mixtures containing butanol, butyl acetate and impurities, e.g., biological, such as antibiotic products of inactivation, pigments, and can be used in chemical, pharmaceutical, paint and other industries

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing butylacrylate involving: reaction of acrylic acid with butanol in the presence of water and a catalyst in a reactor; where the starting material is an aqueous solution of acrylic acid which is at least one of: (1) condensed water, obtained from vapour used in a kinetic vacuum pump which transports gas after trapping fluid process medium- vapour which is blown at high speed, (2) water for hydraulic sealing in a liquid ring pump which isolates liquid-water after air is let into the housing, (3) water used for collecting acrylic acid in the device which collects acrylic acid from an acrylic acid-containing gas, and acrylic acid which is not present in the aqueous solution of acrylic acid, where the device used for collecting acrylic acid is one or more devices selected from a group comprising a packed column, a plate-type column, a spray column and a scrubber. The invention also relates to a method of producing a super-absorbing polymer based on acrylic acid, involving the following steps: polymerisation of acrylic acid, in which the aqueous phase used is an emulsified aqueous solution of an acrylic acid monomer and water, dehydration of the obtained mixture during azerotropic distillation, where the starting material is aqueous acrylic acid solution which is at least one of the following: condensed water obtained from vapour used in a kinetic vacuum pump which transports gas after trapping fluid process medium - vapour, which is blown at high speed, water for hydraulic sealing in a liquid ring pump which isolates liquid-water after air is let into the housing, water used for collecting acrylic acid in the device which collects acrylic acid from an acrylic acid-containing gas, and acrylic acid which is not present in the aqueous solution of acrylic acid, where the device used for collecting acrylic acid is one or more devices selected from a group comprising a packed column, a plate-type column, a spray column and a scrubber.

EFFECT: design of an efficient method of using aqueous solution of (meth)acrylic acid with low concentration, formed at the stage for producing/storing (meth)acrylic acid.

13 cl, 2 ex

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