Catalyst to obtain chloroform and chlorinated paraffin wax and a method of producing chloroform and chlorinated paraffin wax

 

(57) Abstract:

The invention relates to a process for the simultaneous receipt of chloroform and chlorinated paraffin wax and catalysts used to produce it. The invention consists of a catalyst to obtain chloroform and chlorinated paraffin wax-based complex copper compounds and nitrogen-containing organic compounds, comprising the following components, wt.%: salt of copper (I) or copper (II) 1,5-4,0; Quaternary ammonium salt, or an amino acid, or amide, or alkanolamine, or urea or its derivative, or a mixture 30,0-50,0; alcohol or hydroxyl-containing organic compound, or water the rest, as well as in the method of producing chloroform and chlorinated paraffin wax, including the hydrogenation of carbon tetrachloride n-paraffins or mixtures thereof in the liquid phase at a temperature of 150-170°C in the presence of a catalyst based on a complex copper compounds and nitrogen-containing organic compounds with subsequent distillation of the chloroform, in which the hydrogenation is carried out at a molar ratio of carbon tetrachloride : paraffin, equal to not less than 1:1, respectively, and the process is conducted in the presence of 1-10 wt.% the above catalyst. Technical result: the creation of kataliticheskaya and high yield of target products to improve their quality. 2 N. and 8 C.p. f-crystals, 1 table.

The invention relates to a process for the simultaneous receipt of chloroform and chlorinated paraffin wax and catalysts used to produce it.

Chloroform is widely used in modern technology as intermediate in obtaining a variety of compounds, including sonneratiaceae freons, and also as a solvent. Chlorinated higher paraffins are used as plasticizers for polymeric materials, in particular polyvinyl chloride, in the production of plastic products, artificial leather, rubber-technical products, as components of paints, lubricants, adhesives and coatings.

Known catalyst for the hydrogenation of carbon tetrachloride higher paraffins, which is a product of the interaction of copper chloride (I) with caprolactam or dimethylformamide, supported on a carrier, and the content of copper chloride (I) is 1-7 wt.% from the mass media. As the carrier using silica gel and a mass ratio of copper chloride (I) and dimethylformamide or caprolactam at drawing is 1:50-200 respectively [RF patent №2107544, publ. 27.03.1998,].

The disadvantage of this catalyst is NISMO painted. To produce a marketable product requires vacuum distillation of the reaction mass, which greatly complicates and increases the cost of the technology process in General. In addition, the catalyst does not provide a high selectivity at high conversion of the raw material. So, when the conversion of paraffin 70-80% selectivity for chloroform does not exceed 97%.

A method of obtaining chloroform by hydrogenation of carbon tetrachloride by molecular hydrogen in the liquid phase at a temperature of 70-180°C in the presence of catalysts based on platinum, with the addition of other metals on alumina [European patent No. 1201300, publ. 2001].

The disadvantages of the method are the complexity of the technology associated with the use of flammable and explosive hydrogen at high temperatures, low of 85% and less selectivity for the chloroform, as well as unproductive consumption part contained in carbon tetrachloride chlorine. More than 30% last used to receive contaminated with organic substances and not representing a commercial value of hydrogen chloride and methane. In addition, the use in the catalyst of precious metals increases the cost of the process.

Also known is a method of obtaining chloro is under catalyst, consisting of one element selected from the group of ruthenium, rhodium, palladium and platinum and at least one additional element selected from the group: copper, silver, gold, taken in an amount from 0.01 to 50 wt.%.

The process is carried out at a temperature from 0 to 200°C.

The disadvantages are the same as the described above is the use of precious metals in the catalyst and a waste of parts of chlorine.

A method of obtaining chloroform by hydrogenation of carbon tetrachloride normal C10-C15paraffin or mixtures thereof in the presence of a catalyst complex compound of copper chloride (I) with caprolactam on solid media.

When this process is carried out at a temperature of 150 to 200°C, contact time 3-16 hours at a molar ratio of carbon tetrachloride and paraffin, equal (2:6): 1, respectively [RF patent №2107678, publ. 27.03.1998,].

The disadvantage of this method is low as it allows for a target product - chloroparaffin. Chloroparaffin contains resin, intensely colored. To produce a marketable product requires vacuum distillation of the reaction mass, which greatly complicates and workovers of raw materials, it is 95-97%. Higher values can be obtained only at low degrees of conversion.

The closest analogue to the described method according to the essence and the achieved technical result is a method for chloroform and chlorinated paraffin wax by hydrogenation of carbon tetrachloride n-paraffins C10-C15or mixtures thereof in the liquid phase at a temperature of 150 to 180°C in the presence of a catalyst complex of chloride copper chloride Quaternary ammonium salts of General formula (R3)(R1)NCl or (R2)(R1)2NCl, where R is a C1-C18-alkyl, R1 - C1-C18-benzyl or formula (R)-CH[N(R1)3CH[N(R1)3-(R2)Cl2], where R2Is h or lower alkyl, a R, R1have the above values, with the molar ratio of Quaternary ammonium salts and copper is 1-10:1, respectively [RF patent №2187489, publ. 20.08.2002,].

The main disadvantage of this method, as the number described above, is the low quality of target products associated with a high content of resinous substances. This raises the need for time-consuming purification using high vacuum distillation, which complicates the technology process is auchenia of chloroform and chlorinated paraffin wax, providing along with the simplification of technology and high yield of target products to improve their quality.

The task is solved by a catalyst to obtain chloroform and chlorinated paraffin wax containing complex copper compounds and nitrogen-containing organic compounds, as compounds of copper includes copper (I) or copper (II) chloride or bromide or carboxylate, as a nitrogen-containing organic compound is a Quaternary ammonium salt, or an amino acid, or amide, or alkanolamine, or urea or its derivative, or a mixture thereof and optionally contains alcohol or hydroxyl-containing organic compound, or water in the following ratio of components (wt.%):

Salt of copper (I) or copper (II) 1,5-4,0

Quaternary ammonium salt,

or amino, or amide,

or alkanolamine, or urea,

or its derivative, or a mixture 30,0-50,0

Alcohol or hydroxyl-containing

Organic compound, or water the Rest

When the catalyst contains a Quaternary ammonium salt of the formula [NR1R2R3R4]+X-where R1and R4- different or identical substituents, wybran>the ri that X-in the Quaternary ammonium salt is a chloride or bromide, or an alcoholate.

Either the catalyst contains amino acids selected from the group of: threonine, asparagine, hydroxyproline, betaine, cysteine, serine.

Or it contains an amide selected from the group: formamid, acetamin, dimethylformamide, dimethylacetamide, caprolactam.

Either it contains alkanolamine, selected from the group of mono, di, and triethanolamine, or their hydroxides, di-(2-hydroxyethyl) dodecylamine.

The catalyst may contain a mixture of at least two nitrogen-containing organic compounds of these groups.

Additionally it contains alcohol, selected from the group of methanol, ethanol, isopropanol.

Either as a hydroxyl-containing organic compounds it contains phenol or alkyl phenol.

Either as a hydroxyl-containing compounds it contains water.

The task is also solved by a method of producing chloroform and chlorinated paraffin wax, including the hydrogenation of carbon tetrachloride n-paraffins or mixtures thereof in the liquid phase at a temperature of 150-170°C in the presence of a catalyst based on a complex copper compounds and nitrogen-containing organizedalphabetically carbon : paraffin, equal to not less than 1:1, respectively, and the process is conducted in the presence of 1-10 wt.% catalyst composition (wt.%):

Salt of copper (I) or copper (II) 1,5-4,0

Quaternary ammonium salt,

or amino, or amide,

or alkanolamine, or urea,

or its derivative, or a mixture 30,0-50,0

Alcohol or hydroxyl-containing

Organic compound, or water the Rest

When the hydrogenation is carried out for 3-12 hours.

The technical result is obtained when using the above-described invention is to substantially improve the quality of chloroparaffin.

The product is colorless or has a faint yellowish or brownish color, contains almost no tar and hydrogen chloride and can be used in the technique without additional purification. The elimination of complex operations on its separation and purification, including known methods, vacuum distillation and other complex procedures, significantly reduces the cost of chloroparaffin and simplifies the technology of its production. An additional advantage provided by the newly proposed catalyst is to achieve 100% selectionist the>To a mixture of 10 ml of water, 20 ml of ethanol and 12 g of compound (I, R1R2is methyl, R3is benzyl, R4- dodecyl, X-C1) add 1 g ul2. Is the dissolving of salt, as evidenced by the appearance of intense green color of the solution. The result is a catalyst of the following composition: ul2- 2.6%, dimethylmethyleneammonium - 30.9%, water - 25.8%, ethanol - 40.7% (catalyst A).

Similar were obtained by the catalysts of the following structures:

Century ul-3%, tributylphosphate - 47%, ethanol 50%

C. ul2to 2.5%, tetrabutyltin - 30% propanol - 67,5%

D. CuCl2- 3%, tributylphosphate - 47%, water 50%

That is, CuCl22.5%, and cysteine is 47.5% ethanol - 50%

F. CuCl2to 3.5%, dimethyl acetamid - 46.5 per cent, propanol - 50%

G. CuCl22.5%, and caprolactam is 47.5%, isopropanol - 50%

N. CuCl - 3%, urea - 42%, phenol - 55%

I. the Acetate of copper (I) - 4%, tributylammonium - 30%, diethanolamine - 20%, water - 46%

J. CuBr (1.5%), tributylammonium - 50%, ethanol - 48,5%

K. CuBr - 3%, tetrabutylammonium-ataxic - 50%, ethanol - 47%

L. ul22.5%, and di-(2-hydroxyethyl)dodecylamine 50%, ethanol is 47.5%

N. CuCl22.5%, and di-erode, 4 ml of a mixture of n-paraffin composition (2:1)

Tridecan 13,3%

Tetradecane 38,8%

Pentadecane 33,7%

Hexadecan 12,2%

Heptadecan 2,0%

and 0.36 ml (3% vol.) liquid catalyst A. the Autoclave is closed, purge with nitrogen, heated to 160°C and maintained at this temperature for 6 hours.

Then the autoclave is cooled to room temperature and opened. Distilled 1.1 ml (1.6 g) of chloroform and 6.7 ml (10.7 g) unreacted carbon tetrachloride. The residue is passed through a 10-cm layer of silica gel. Get to 2.6 ml of chloroparaffin representing a viscous light colored liquid with a brownish tinge. The chlorine content in the product is 13.1%, the selectivity of transformation of carbon tetrachloride in chloroform - 100%.

Similarly conduct further experiments, the results of which are presented in the table.

As can be seen from the table, the selected process conditions are optimal. Pets decrease excess of carbon tetrachloride, which, however, leads to a decrease of the yield of the target product. The temperature rise above the proposed interval 150-170°With impractical because not lead to a significant growth in the but, as it leads to irrational consumption of reagents without achieving a positive effect. The increase in the process time of more than 12 hours is also impractical because it leads to deterioration of the quality of chloroparaffin. Comparative experience 21 in which the catalyst does not contain hydroxyl-containing compounds, shows the impossibility of achieving high quality chloroparaffin determined by chlorine and color, without using simultaneously all components of the proposed catalyst.

The use of the invention enables the simultaneous receipt of chloroform and chlorinated paraffin wax in a single process, without the use of molecular chlorine.

Such processes are developed in recent years due to their obvious benefits - environmental, safety, opportunities to utilize not used after the signing of agreements on the protection of the ozone layer carbon tetrachloride, making full use of the introduced reaction of chlorine to obtain valuable products.

1. Catalyst to obtain chloroform and chlorinated paraffin wax containing complex copper compounds and nitrogen-containing organic the IDA, or bromide, or carboxylate as a nitrogen-containing organic compound is a Quaternary ammonium salt, or an amino acid, or amide, or alkanolamine, or urea or its derivative, or a mixture thereof and optionally contains alcohol or hydroxyl-containing organic compound, or water in the following ratio of components, wt.%:

Salt of copper (I) or copper (II) 1,5-4,0

Quaternary ammonium salt, or

amino acid, or amide, or

alkanolamine, or urea, or

derivative, or a mixture 30,0-50,0

Alcohol or hydroxyl-containing

organic compound, or water the Rest

2. The catalyst p. 1, characterized in that it contains a Quaternary ammonium salt of the formula [NR1R2R3R4]+X-where R1and R4- different or identical substituents selected from the group of Akilov, arylalkyl, cycloalkyl, hydroxyalkyl; R2is methyl; R3is benzyl, and X-in the Quaternary ammonium salt is a chloride or bromide, or an alcoholate.

3. The catalyst p. 1, characterized in that it contains amino acids selected from the group of threonine, asparagine, hydroxyproline, buy formamid, the ndimethylacetamide, dimethylformamide, dimethylacetamide, caprolactam.

5. The catalyst p. 1, characterized in that it contains alkanolamine selected from the group of mono, di, and triethanolamine or their hydroxides, di-(2-hydroxyethyl)dodecylamine.

6. The catalyst p. 1, characterized in that it comprises a mixture of at least two nitrogen-containing organic compounds.

7. The catalyst p. 1, characterized in that it contains an alcohol selected from the group of methanol, ethanol, isopropanol.

8. The catalyst p. 1, characterized in that it contains as a hydroxyl-containing organic compounds phenol or alkyl phenol.

9. The method of producing chloroform and chlorinated paraffin wax, including the hydrogenation of carbon tetrachloride n-paraffins or mixtures thereof in the liquid phase at a temperature of 150-170°C in the presence of a catalyst based on a complex copper compounds and nitrogen-containing organic compounds with subsequent distillation of the chloroform, characterized in that the hydrogenation is carried out at a molar ratio of carbon tetrachloride:paraffin wax no less than 1:1, respectively, and the process is conducted in the presence of 1-10 wt.% catalyst composition, wt.%:

Salt of copper (I) or copper (II) 1,5-4,0

its derivative, or a mixture 30,0-50,0

Alcohol or hydroxyl-containing

organic compound, or water the Rest

10. The method according to p. 10, characterized in that the hydrogenation is carried out for 3-12 hours



 

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