Catalyst and method shown in fig chloroaromatics connections

 

Usage: petrochemistry. The inventive liquid-phase hydrodechlorination chloroaromatics compounds is performed on the catalyst includes palladium with the addition of precious metals - platinum, ruthenium, or transition metals such as iron, cobalt or mixtures thereof. The catalyst contains palladium in an amount of not higher than 1 wt.%, platinum, ruthenium in an amount of not higher than 1 wt. percent, iron, cobalt or mixtures thereof in an amount of not less than 1 wt.%. The process of the phase transfer agent and reductant NaBH4in water-ethanol medium at a molar ratio of components chloroaromatics connection (S-S1): palladium with the addition of precious metals - platinum, ruthenium, or transition metals such as iron, cobalt or mixtures thereof: NaBH4=50-1000:1:3. As the phase transfer agent use tetramethyllead ammonium, tetraethyllead ammonium hydroxide of tetraethylammonium, Aliqvat. Technical result: development of a method of hydrodechlorination using smaller quantities of catalyst and reducing agent NaBH4while maintaining a high degree of transformation of chlorinated aromatic compounds. 2 s and 5 C.p. f-crystals, 1 table.

The invention relates to FPIC is triticeae hydrodehalogenation (GDH) kaleidoscopically compounds is a complex scientific issue, combining fundamental and applied aspects. Fundamental aspects of the task or fine organic synthesis are selective GDH variety of organic compounds in the absence of a reducing impact on other functional fragments of molecules. Recently come to the forefront practical aspects of the implementation of GDH in connection with the ever increasing environmental pollution toxic malodorants connections.

Stringent environmental and economic constraints imposed on modern production halogenorganics products, determine the number of claims to methods of recycling these productions. These requirements include: renewable carbon-containing raw material or commercial value of the resulting products, efficiency of processing, a high degree of conversion, the versatility of the method, the absence among the products of toxic substances.

There are various methods of disposal of polygalacturonase compounds: chemical and electrochemical dechlorination, thermal, photo - and radiation-chemical, biotechnological methods, oxidation and hydrogenolysis.

Reagent methods DEH is the train they are characterized by rapid deterioration of the equipment, working in aggressive environments at high temperatures, which limits their industrial application.

Prospects of implementation of electrochemical methods [L. B. Zanaveskin, C. A. Averianov. USP 67 (8), 1998] industry is also small due to the insufficiently high conversion and high requirements to the purity of the original polygalacturonase connections.

Pyrolytic methods [K. W. Lee, W. R. Schofield, D. S. Lewis, Chem. Eng., (USA) 71 (7) (1984) 46] have a high cost due to the large energy consumption of these processes and poor environmental performance. In addition, these methods malaysiaceline and therefore unsuitable for dechlorination materials with a low content of chlororganic. To some extent, these shortcomings are overcome through the use of catalytic pyrolysis, however, the formation of pyrolytic carbon leads to rapid deactivation of the catalysts [L. B. Zanaveskin, C. A. Averianov, Y. A. Traeger. USP 65 (7), 1996].

Methods for radiation and photochemical dechlorination [T. Sawai, Y. Shinozaki, Chem. Lett. 865 (1972)] currently nizkoprofilnym and require high energy costs.

Methods biodegradation [M. A. Mousa, J. F. Quensen, K. Chou, S. A. Boyd, Environ. Sci. Technol. 30 (1996) 2087] is only effective in the CRL by other methods. Another issue is the viability of destructive polychlororganic microorganisms in the soil, where they need to effectively compete with soil microorganisms.

The method of thermal incineration [L., Kokoszka, J. Flood, Chem. Eng. 92 (1985) 41] also unsuitable today, as it leads to the formation of highly toxic products such as chlorine, nitrogen oxides, phosgene, and dioxins. In addition, thermal incineration requires a lot of fuel, leads to irreversible loss of hydrocarbons, the selection in the environment of carbon dioxide and rapid wear of the equipment. Most of these shortcomings deprived of a method of catalytic combustion. However, despite significant progress in the development of new catalytic systems for combustion processes halogenorganics waste, the range of objects neutralization remains relatively narrow. Obviously this method cannot be considered as promising as the irreversible loss of the material during its implementation is not consistent with the concept of low-waste technologies.

The most versatile and promising method of processing and disposal halogenorganics waste can be considered hydrodehalogenation, or hydrogenolysis. This obul conditions until complete conversion of the original organic reagent. Secondly, the reaction of the election in respect of the object of processing, which allows you to successfully carry out the dechlorination of organochlorine compounds in any range of their concentrations. Thirdly, when the hydrogenolysis eliminates the formation of secondary pollutants. Fourth, this method has an obvious saving in nature.

Hydrogenolysis halogenorganic is possible to carry out thermal, catalytic and conventional chemical method [L. B. Zanaveskin, C. A. Averianov. USP 67 (8), 1998]. Thermal hydrogenolysis requires high energy costs. The latter method requires expensive donors of hydrogen is rather preparative and cannot be considered as the basis for industrial implementation. Greatest practical importance of liquid-phase catalytic reductive dechlorination carried out in mild conditions.

Catalytic HDC halogenated aromatic compounds, in particular chlorides, very important reaction because it allows you to process many toxic organic compounds into the corresponding hydrocarbons without waste. Chlorobenzene can be converted into benzene using different systems. It is shown that n is ineni is palladium [C. A. Marques, M. Selva, P. Tundo, J. Org. Chem. 58 (1993) 5256] . The main feature of palladium, which makes him stand out from a number of active HDC in metals, is the ability to absorb hydrogen in large quantities and activate it.

In the processes HDC catalysts are deactivated Hcl, this effect is due to the strong interaction between hydrogen halides and metal [D. J. Moon, M. J. Chung, K. Y. Park, S. I. Hong, Appl. Catal. A 168 (1998) 159]. The study of the phenomena of deactivation, regeneration of the deactivated catalyst and the creation resistant to poisons catalytic systems is of great practical importance and is widely studied. The negative effect of the presence formed in the system Hcl may be neutralized by the use of acceptors of protons, for example NaOH, NH3and like them. Modification of the deposited palladium catalysts or carriers compounds Na increases their resistance to otravlyayuscikh the action of Hcl and increases the service life of the catalytic reactions HDC [M. A. Aramendia, R. Burch, I. M. Garcia, A. Marinas, J. M. Marinas, B. W. L. Souhtward, F. J. Urbano, Appl. Catal. 31 (2001) 163-171].

The closest analogue to the invention, the technical essence and the achieved result can serve as a way dechlorination chloroaromatics compounds in prisutstvie the S.% compared to Ni, on carbon carriers and reductant NaBH4in the ethanol or atenolo-toluene (60:40) environment at t=20-40oS, RH2=1 ATM in the presence of 10% NaOH solution (to bind Hcl) at a molar ratio of components polychromatically connection (PHA) (C-CL) : Kt (Ni or Ni-promoted Pd) : NaBH4=1:0.03 to 50:1-350 [RU, patent 2100338, C1, CL 15/12 C 07 C, 15/14, 1997]. When using such a composition to a high degree of conversion (70-100%) achieved 3-6 hours

The disadvantages of the prototype are: large number of NaBH4and the deposited metal with respect to the substrates; rather low activity of the catalysts in the dechlorination reaction.

The invention solves the task of developing a simple and convenient method of recycling of chlorinated aromatic compounds which can reduce the amount of used catalyst and NaBH4.

The problem is solved using the cheaper than NaBH4molecular hydrogen as a hydrogenating reagent and catalyst, consisting of a deposited on a carbon carrier Pd promoted noble (Pt, Ru) or transitional (Fe, Ni, Co) metals in different mass ratios when the total number of metals in the catalyst 1-3 m the l ammonium chloride, tetraethyl ammonium chloride, tetraethyl ammonium hydroxide, Aliquat [C. A. Marques, M. Selva, P. Tundo, J. Org. Chem. 58 (1993) 5256].

The catalyst contains palladium in an amount of not higher than 1 wt.%, platinum, ruthenium in an amount of not higher than 1 wt.%, iron, cobalt or mixtures thereof in an amount of not less than 1 wt.%.

This composition allows the process of dechlorination chloroaromatics compounds dissolved in toluene and isopropanol, under mild conditions t= 20-55oS, RH2=1 ATM at a molar ratio of components chloroaromatics connection (C-CL) : Kt (Pd additives noble (Pt, Ru) or transient (Fe, Co, Ni or mixtures thereof) : NaBH4=50-1000:1:3, and the highest conversion rates (80-100%) are achieved in 1-3 hours. The addition of catalyst is calculated so as to satisfy a certain ratio between the number of deposited metals and the amount of the substrate.

In the work as a media carbon media Sibunit. In this work Sibunit is a three-dimensional matrix with a specific surface area of 370 m3/g (BET), a density of 2.9 g/cm3with a pore volume of 0.4 cm3/g, with developed micropore volume of 0.15 cm3/g, in which the processes of adsorption and catalysis. Canreduce reaction.

The hydrodechlorination catalysts prepared by deposition of the precursors of the active component (chlorides of metals from solutions to the media with constant stirring and heating. Then carry out the drying catalysts at 130-150oWith over five hours. The catalyst is reactivated by tetrahydroborate sodium in water-ethanol solution at a ratio (Pd additives noble (Pt, Ru) or transient (Fe, Co, Ni or mixtures thereof) : NaBH4= 1:3.

Salient features of the invention are: the use of catalysts comprising deposited on carbon carriers Pd promoted noble (Pt, Ru) or transitional (Fe, Ni, Co) metals in different mass ratios; conducting hydrodechlorination of chlorinated aromatic compounds in a ratio of components chloroaromatics connection (C-CL) : Kt (Pd additives noble (Pt, Ru) or transient (Fe, Co, Ni or mixtures thereof) : NaBH4=50-1000:1:3; conducting hydrodechlorination of chlorinated aromatic compounds in the presence of interfacial agents.

In all following examples, the analysis of the reaction products is carried out by gas chromatography on a chromatograph of Cves, the column length of 3 meters, a diameter of 2.5 mm, was filled with 5% SE-30 supported on Chromaton N-AW.

In the use of ethanol-water and toluene-isopropanol solutions, 50% KOH solution (for binding emitted Hcl), chlorobenzene, hexachlorobenzene, tetramethyl ammonium chloride. The reaction product using chlorobenzene is benzene, using hexachlorobenzene main product is benzene with impurities, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene and pentachlorobenzene.

The invention is illustrated by the following examples.

Example 1. The reactor is placed a portion of the catalyst 3 wt.% (Pd+Fe)/C (ratio of Pd:Fe=20:80 by weight), carbon material Sibunit with the following parameters:beats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3containing 0,1794 mmol of metal, and a portion of NaBH4(0,5382 mmol) dissolved in 5 ml of ethanol-water mixture. After recovery of the catalyst it is washed with a small amount of water, pour 4 ml of 50% KOH solution, add a phase transfer catalyst (CH3)4NCl and activate with stirring in the th in 11 ml of the organic phase, consisting of 4 ml of isopropanol and 7 ml of toluene. The system is intensively stirred at a constant temperature in hydrogen atmosphere.

Example 2. The reaction is carried out under conditions analogous to example 1, in the presence of catalyst 3 wt.% (Pd+Fe)/C (ratio of Pd:Fe=10:90 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 3. The reaction is carried out under conditions analogous to example 1, in the presence of catalyst 3 wt.% (Pd+Fe)/C (ratio of Pd:Fe=5:95 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 4. The reactor is placed a portion of the catalyst 3 wt.% (Pd+Co)/(the ratio of Pd: With= 20: 80 by weight), carbon material Sibunit with the following parameters:beats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3), the soda is the formation of the catalyst it is washed with a small amount of water, pour 4 ml of 50% KOH solution, add a phase transfer catalyst (CH3)4NCl and activate with stirring in an atmosphere of hydrogen for one hour. In the system add 1,495 mmol C6CL6(8,97 mmol C-CL), dissolved in 11 ml of the organic phase, consisting of 4 ml of isopropanol and 7 ml of toluene. The system is intensively stirred at a constant temperature in hydrogen atmosphere.

Example 5. The reaction is carried out under conditions analogous to example 4, in the presence of catalyst 3 wt.% (Pd+Co)/(the ratio of Pd:Co=10:90 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 6. The reaction is carried out under conditions analogous to example 4, in the presence of catalyst 3 wt.% (Pd+Co)/(the ratio of Pd:Co=5:95 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 7. The reactor is placed a portion of the catalyst 1 wt.% (Pd+Co)/2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3containing 0,0897 mmol of metal, and a portion of NaBH4(0,2691 mmol) dissolved in 5 ml of ethanol-water mixture. After recovery of the catalyst it is washed with a small amount of water, pour 4 ml of 50% KOH solution, add a phase transfer catalyst (CH3)4NCl and activate with stirring in an atmosphere of hydrogen for one hour. In the system add 8,97 mmol C6H5CL dissolved in 11 ml of the organic phase, consisting of 4 ml of isopropanol and 7 ml of toluene. The system is intensively stirred at a constant temperature in hydrogen atmosphere.

Example 8. The reaction is carried out under conditions analogous to example 7, in the presence of catalyst 1 wt.% (Pd+Co)/(the ratio of Pd:With=20:80 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 9. The reaction is carried out under conditions analogous to example 7, in the presence of catalyst 1 wt.% (Pd+Co)/(saotng (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 10. The reactor is placed a portion of the catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd: Pt=95:5 by weight), carbon material Sibunit with the following parameters:beats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g of micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3containing 0,00897 mmol of metal, and a portion of NaBH4(0,02691 mmol) dissolved in 5 ml of ethanol-water mixture. After recovery of the catalyst it is washed with a small amount of water, pour 4 ml of 50% KOH solution, add a phase transfer catalyst (CH3)4NCl and activate with stirring in an atmosphere of hydrogen for one hour. In the system add 1,495 mmol C6CL6(8,97 mmol C-CL), dissolved in 11 ml of the organic phase, consisting of 4 ml of isopropanol and 7 ml of toluene. The system is intensively stirred at a constant temperature in hydrogen atmosphere.

Example 11. The reaction is carried out under conditions analogous to example 10, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=90:10 by weight), carbon motarjem micropores - 0.15 cm3/g, average pore sizedensity -2,9 g/cm3).

Example 12. The reaction is carried out under conditions analogous to example 10, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=85:15 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d= 0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 13. The reaction is carried out under conditions analogous to example 10, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=50:50 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, the volume of micropar - 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 14. The reaction is carried out under conditions analogous to example 10, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=10:90 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

beats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3containing 0,00897 mmol of metal, and a portion of NaBH4(0,02691 mmol) dissolved in 5 ml of ethanol-water mixture. After recovery of the catalyst it is washed with a small amount of water, pour 4 ml of 50% KOH solution, add a phase transfer catalyst (CH3)4HCl and activate with stirring in an atmosphere of hydrogen for one hour. In the system add 8,97 mmol C6H3CL dissolved in 11 ml of the organic phase, consisting of 4 ml of isopropanol and 7 ml of toluene. The system is intensively stirred at a constant temperature in hydrogen atmosphere.

Example 16. The reaction is carried out under conditions analogous to example 15, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=85:15 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 17. The reaction is carried out under conditions analogous to example 15 is th the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizedensity -2,9 g/cm3).

Example 18. The reaction is carried out under conditions analogous to example 15, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=65:35 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 19. The reaction is carried out under conditions analogous to example 15, in the presence of catalyst 1 wt.% (Pd+Pt)/C (ratio of Pd:Pt=50:50 by weight), carbon material Sibunit with the following parameters: Sbeats=370 m2/g (BET), d= 0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore sizethe density of 2.9 g/cm3).

Example 20. The reactor is placed a portion of the catalyst 1 wt.% (Pd+Ru)/C (ratio of Pd: PT= 20: 80 by weight), carbon material Sibunit with the following parameters:beats=370 m2/g (BET), d=0.5 mm, a pore volume of 0.4 cm3/g, micropore volume is 0.15 cm3/g, average pore size

Based on the above results we can conclude that the proposed method of carrying out the reaction of hydrodechlorination chloroaromatics compounds, which are summarized in the table has the following advantages: conducting the hydrodechlorination reaction when using smaller quantities of catalyst and reducing agent - NaBH4while maintaining a high degree of transformation of chlorinated aromatic compounds; the use of highly active bimetallic supported catalysts that are resistant to otravlyayuscikh step formed in the reaction of Hcl.

Claims

1. The catalyst of liquid-phase hydrodechlorination chloroaromatics connections on the Dios with the addition of noble metals platinum, ruthenium or transition metals such as iron, cobalt or mixtures thereof.

2. The catalyst p. 1, characterized in that it contains palladium in an amount of not higher than 1 wt.%.

3. The catalyst PP.1 and 2, characterized in that it contains platinum, ruthenium in an amount of not higher than 1 wt.%.

4. The catalyst PP.1 and 2, characterized in that it contains iron, cobalt or mixtures thereof in an amount of not less than 1 wt.%.

5. The method shown in Fig chloroaromatics compounds, which consists in the fact that the process of liquid-phase hydrodechlorination is carried out in the presence of a heterogeneous catalyst, of the phase transfer agent and reductant NaBH4, wherein the process is carried out in the presence of a catalyst according to any one of paragraphs.1-4 in water-ethanol medium at a molar ratio of components chloroaromatics connection (S-S1): palladium with the addition of precious metals - platinum, ruthenium, or transition metals such as iron, cobalt or mixtures thereof: NaBH4=50-1000:1:3.

6. The method according to p. 5, characterized in that as the phase transfer agent use tetramethyllead ammonium, tetraethyllead ammonium hydroxide of tetraethylammonium, Aliqvat.

7. The method according to PP.4 and 5, characterized in that the process is executed p

 

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