The regeneration process of the copper-vanadium catalyst from the mother solutions of adipic acid production

 

(57) Abstract:

The present invention relates to the basic organic synthesis and can find application in the technology of producing adipic acid. The regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid at elevated temperatures in the presence of copper-vanadium catalyst is carried out by concentrating the mother solutions by evaporation to obtain a residue containing lower dicarboxylic acids WITH4- C6salts of copper and vanadium, and the residual amount of nitric acid and water, separation of copper and vanadium on the catalyst and return it to the stage of oxidation, the allocation of low-dicarboxylic acids WITH4- C6at low temperature. The difference of the proposed method lies in the fact that the mother solution, one stripped off before the contents of the lower dicarboxylic acids WITH4- C665 to 75 wt.%, mixed with mother liquor stage Chris - tallization lower dicarboxylic acids WITH4- C6when mass - tion ratio of the remainder: Royal 1 : 1 solution of 1.5 obtained WM - pensio is subjected to crystallization at SUB> - C6separated, and the resulting mother liquor is separated into two streams, one of which is directed to razbam of balance, and the other return to the stage of oxidation.

Sawse - range of the method allows to obtain a regenerated catalyst more question - th method with a high degree of extraction and disposed dicar - oil acid C4- C6in the form of their mixtures. 1 Il., table 1.

The invention relates to the primary organic synthesis, in particular to methods of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation cyclohexanol and/or cyclohexanone with nitric acid and may find application in the manufacture of adipic acid, which is the raw material for the production of polyamide-66, ester plasticizers, poliuretano etc.

There is a method of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid, which consists in the fact that the mother liquor obtained after crystallization of adipic acid, is subjected to the evaporation of water and nitric acid to the solid residue. This mixture costo, the mistakes of water and nitric acid, a component of the copper-vanadium catalyst (copper salts and vanadium), and impurities (mainly iron and others). This mixture is treated with sulfuric acid (or phosphoric), and then filtering or centrifuging at a temperature of 80 - 160oC allocate catalyst; organic residue is burned and the resulting gases are used to preheat privelage stock solution (1).

The disadvantage of this method lies in the fact that the components of the catalyst of copper and vanadium are allocated in the form of sulfates or phosphates, which return to the process without taking into nitrates can adversely affect the quality of the finished product. In addition, the filter conditions require special sophisticated equipment (filter or centrifuge heated).

There is a method of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid in which from the mother solution is distilled under vacuum excess acid without allocating a catalyst. The resulting mixture fractionary, and the residue containing the catalyst recycle to the reaction apparatus 3 (2).the study, products which remain in Cuba together with the components of the catalyst, and the products of corrosion of the equipment (salts of iron and other). To return such a complex mixture in the beginning of the process is impossible without compromising the quality of the main product.

According to the method (3) the mother liquor formed during the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid, is treated with alkanols and water-immiscible solvent in order to extract the formed esters of dibasic4- C6acids. The organic and aqueous phases are separated. From the organic phase by distillation produce dialkyl ethers of aliphatic dicarboxylic acids WITH4C6. The aqueous phase is distilled to separate the excess alkanol and water. The residue containing nitric acid and the catalyst returns to the stage of oxidation.

However, the addition of alkanol unsafe, because at high concentrations of nitric acid can develop his uncontrolled oxidation and the formation of explosive and highly toxic alkylnitrates. The disadvantages of the method include a significant complication of the whole process flow, due to the need for the solvent and other

There is a method of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid, which consists in the fact that the mother liquor is subjected to distillation under reduced pressure to remove the nitric acid to the residue water is added to maintain the pH of the solution is 1.5 to 6.0, and the resulting solution passed through an ion-exchange resin to precipitate copper and vanadium. Precipitated copper and vanadium is removed from the resin by washing with nitric acid (4).

The method has the following disadvantages:

1) to maintain the pH of the medium required large dilution, resulting in increased volumes of wastewater;

2) in the mother solution along with copper and vanadium is iron, which is also captured by the ion exchange resin. The return of catalyst to the stage of oxidation without separation of iron leads to the accumulation of the latter, and consequently the quality of adipic acid.

There is a method of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid, involving the evaporation of motocr cooled to 60oC. the precipitation of organo-vanadium complex is separated from the solution containing the copper, by filtration. The filtrate is diluted with water and passed through an ion-exchange resin, which adsorb copper ions. For elution of the latest and regeneration of the resin used 8% nitric acid (5).

The described method disadvantages of method (4).

These disadvantages can be eliminated by using (6), whereby the regeneration of the cation exchange resin is carried out in two stages: first, the cation exchange resin is treated with 0.1 to 0.5 N. nitric acid for excretion in the solution of copper ions and vanadium, which return in the process, and then 1 5 N nitric acid to remove iron ions. But this method has drawbacks related to the fact that the process produces large quantities of nitric acid, nitrate of iron, the output of which process requires energy-intensive stage of the distillation of nitric acid and its concentration.

According to the method (7) the mother liquor obtained after crystallization and separation of adipic acid, is subjected to evaporation and receive the residue containing dibasic acid C4C6and ions of copper and vanadium. Nitric acid and water are removed is OK dissolve in water. The ratio of water and the dry residue selected so that the concentration of NDF was not more than 17 wt.

This method has all the disadvantages of the method (4, 5).

The closest population characteristic is the way the regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid, in which the mother liquor obtained after crystallization of adipic acid and nitric acid containing, water and recovered copper-vanadium catalyst, evaporated to remove nitric acid and water. Obtained in the form of water dry residue is treated with a solvent, which is used as the ketones, for extracting the NIR. The resulting suspension is separated liquid phase containing an organic part of the suspension, and a solid phase containing the 97.6 wt. copper-vanadium catalyst. The resulting filtrate is treated under vacuum at a temperature of minus 20oC. the mixture NIR crystallizes. The resulting stock solution was again evaporated to dryness to obtain a precipitate, which return to the beginning of the process (8).

A characteristic feature of the method (8) is that for the Department comoonics (8) there are no data on the distribution of impurities between the crystalline phase NIR and phase of the catalyst. Therefore, it is impossible to judge the degree of risk of contamination of the main product when returning the regenerated catalyst. The main disadvantages of the method are its multi-stage, introduction to process flammable components (ketones), high energy consumption associated with the need for regeneration of the solvent.

The objective of the proposed invention is the creation of such technology regeneration of the copper-vanadium catalyst from the mother solutions of adipic acid production, which is due to the exclusion of flammable solvents in a simple way allows to obtain a regenerated catalyst is not contaminated by impurities, with a high degree of extraction and disposed of dicarboxylic acid WITH4C6in the form of their mixtures.

The problem is solved in that in the method of regeneration of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid at elevated temperatures in the presence of copper-vanadium catalyst comprising a concentration of mother solutions by evaporation to obtain a residue containing the lower dicarba copper-vanadium catalyst and return it to the stage of oxidation, the selection of a mixture of LDA at low temperature, according to the claimed invention, the mother liquor is one stripped off before the NDF content of 65 to 75 wt. mixed with mother liquor phase crystallization of culture in the mass ratio of the residue of the mother liquor 1 1 1,5 obtained suspension is subjected to crystallization at a temperature below (-10)oC, preferably (-10) (-15)oC, the wet crystals NIR separated, and the resulting mother liquor containing 96,0 98,0 wt. the regenerated catalyst is divided into two streams, one of which is directed to the dilution of the residue in the above ratio, and the other representing the remaining after the thinning of a portion of the mother liquor, return to the stage of oxidation. The separated wet NDK crystals are melted at 120 150oC and subsequent crystallization at 40 60oC.

The search, conducted on the sources of scientific, technical and patent information, showed that the combination of all the essential features of the claimed technical solution is unknown. So we can assume that the proposed method of recovery of the copper-vanadium catalyst from the mother solutions of adipic acid production of bootverbose is found that such elements of the technological scheme, the mutual position which allows you to create more simple in comparison with the prototype technology regeneration of the copper-vanadium catalyst from the mother solutions of adipic acid production due to the exclusion from the scheme of the extraction step of the ketone and subsequent energy intensive regeneration of the latter. As was established in the research process, the main amount of color-forming impurities contained in the treated uterine solution, concentrated in the crystalline phase NIR generated during low-temperature crystallization of one stripped off the mother liquor. Due to this circumstance, the return of a solution containing regenerated catalyst to the stage of oxidation of cyclohexanol and/or cyclohexanone does not reduce the quality of the main product.

The advantage of the proposed method in comparison with known methods (1 - 8) is that for its implementation there is no need to resort to the methods of extraction, ion exchange, chemical treatment, which in all cases is accompanied by increasing complexity of the technological scheme, the increase in raw material and energy costs, as well as the formation of value is property of the proposed method is what are the side products of the main reaction (mixture NIR) derived from the process in the form of commodities.

Comparative analysis of the essential distinctive features of the proposed method and the known characteristics shows that a significant distinguishing characteristics used for the first time. And the whole set of essential features of the proposed technical solution allows to obtain a new result is to simplify the method and to get the catalyst not containing impurities with a high degree of regeneration. Thus, we can conclude that the claimed method meets the requirements of inventive step.

The drawing shows a scheme illustrating the proposed method.

The drawing shows the flow: 1 of the original mother liquor, 2, 4 - one stripped off the mother liquor, 3, 8 nitric acid and water, 5 mixed mother liquor, 6 slurry stock solution, 7 wet crystals NIR, 9 crystal mixture NIR, 10 13 stage mother liquor of the crystallization of culture, evaporator 14, a separator 15, 16 of the tank for mixing the solution, the mold 17, 18 of the apparatus for separating crystals, 19 melting-casting mold 20 a collection of mother liquor.

Way to bring transto evaporator 14 and then thread 2 is sent to the separator 15. In the apparatus 14, 15 the mother liquor is evaporated by distillation of nitric acid and water, return flow 3 phase oxidation, and one stripped off the solution flow 4 is sent to the capacity for shifting solutions 16 where it is mixed with the circulating mother liquor. From the tank 16 by a thread 5, the obtained solution is sent to the crystallizer 17, where it is cooled to a 25% solution of CaCl2. Formed in the mold 17, the suspension flow 6 is directed to apparatus for separating crystals 18, where separate wet NDK crystals from the mother liquor. Then the wet crystals NIR stream 7 is sent to the melt-mold 19. In the process of melting of crystals NIR distills the remains of nitric acid and water which flow 8 after the condensation of a return to the stage of oxidation in the form of a solution of nitric acid. The resulting melt mixture of NDF in the same apparatus is subjected to crystallization and system flow 9 remove the crystals of the mixture of culture. After separation of the crystals in the apparatus 18 mother liquor stream 10 is directed into a collection of stock solution 20 and the thread 11 extending from this collection, divided into two streams. One of them (stream 12) is directed to the dilution of the residue in the tank for mixing fluids 16, and Dora to the content of NDF 65 - 75 wt. allows you to have a homogeneous solution at 90oC and a vacuum of 200 mm RT.article.

The selected limit of the mass ratio of one stripped off the remainder of the mother liquor is equal to 1 1 to 1.5, provides the fluidity of the suspension and its transportability.

When using the crystallization temperature NIR excess (-10)oC, in the circuit accumulates glutaric acid because of its high solubility in return to the stage of oxidation of the mother solution. The process of crystallization NIR at temperatures below (-15)oC the degree of crystallization of NIR increases slightly, but the energy consumption increases significantly.

Examples 1 to 3:

1236,44 kg/h of the original mother liquor containing, by weight. NIR - 13,25 (including adipic acid 4,01; glutaric acid 6,56; succinic acid 2,68), nitric acid 49,596; water 36,95; copper 0,16; vanadium 0.04 and iron 0,004; evaporated at a temperature of 90oC and a residual pressure of 200 mm RT.article One stripped off the mother liquor is mixed with the circulating mother liquor having a temperature of (-10) (-15)oC in the ratio 1 to 1 to 1.5. Obtained by mixing the solution with a temperature of 30 40oC sent for crystallization, where it is cooled to Arnie the NDK crystals are melted at 120 150oC. the crystals distills the remains of nitric acid and water, which, after condensation return to the stage of oxidation in the form of a solution of nitric acid. The resulting melt mixture NIR is subjected to crystallization at 40oC and get the NDK crystals that are removed from the system as a commercial product. The part of the mother liquor obtained after low-temperature crystallization of NIR and contain the bulk (96,0 98,0 wt.) catalyst, return to dilute suspension in the above ratio, and the remainder recycled to the stage of oxidation (the main process). The degree of regeneration of the catalyst is 96,0 98,0% and the number with NDK crystals of iron to 68,86% of its initial content in the recycled mother solution. The results of the implementation examples 1 to 3 are presented in the table.

These examples show the possibility of achieving the claimed technical result using the proposed combination of essential features. Namely, due to the low-temperature crystallization of NDF from one stripped off to 65,0 75,0% concentration of the mother liquor to get high-quality solution containing up to 96,0 98,0 mA is enough solution. This solution without additional processing can be returned to the head of the process, because the main number of undesirable impurities (iron and others) presented with NDK crystals.

Therefore, the inventive method of regeneration of the copper-vanadium catalyst from the mother solutions of adipic acid production meets the requirements of industrial applicability.

The regeneration process of the copper-vanadium catalyst from mother solutions for the production of adipic acid by oxidation of cyclohexanol and/or cyclohexanone with nitric acid at elevated temperatures in the presence of copper-vanadium catalyst comprising a concentration of mother solutions by evaporation to obtain a residue containing lower dicarboxylic acids (C4< / BR>
C6salts of copper and vanadium, and the residual amount of nitric acid and water, separation of the copper-vanadium catalyst and return it to the stage of oxidation, the selection of lower dicarboxylic acids mixture C4C6at low temperature, wherein the mother solution, one stripped off before the contents of the lower dicarboxylic acids (C4C665 75 wt. mixed with mother liquor stage of crystallization of the lower decasia is subjected to crystallization at a temperature below -10oWith moist crystals lower dicarboxylic acids (C4C6separated and the resulting mother liquor is separated into two streams, one of which is directed to the dilution of the residue, and the other return to the stage of oxidation.

 

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