The method of producing glodeanu

 

(57) Abstract:

Usage: as solvents, foaming agents in the production of foams, refrigerants. The inventive halodurans raw materials, in particular perchlorethylene, trichlorethylene, dipertahankan, is subjected to interaction with hydrogen fluoride in the liquid phase at elevated temperature and pressure in the presence of petaluridae antimony, optionally containing 13 60 mol. tetrachloride of tin, and the catalyst was pre-treated with hydrogen fluoride at 20 to 150°C. and pressures of 0.1 to 2.3 MPa. 4 C.p. f-crystals, 2 tab.

The invention relates to the production of perchloromethane ethane number of General formula C2F1+NCl4-NH, which are used as solvents, and blowing agents in the production of foams, refrigerants.

Up to the present time as a fluorine-containing solvent widely used trifluorotrichloroethane (PI. 113), and as the foaming agent ferrichloride (PI. 11), as a refrigerant difenilmetan (PI. 12).

However, in accordance with the Montreal Protocol on substances that Deplete the ozone layer and programmes of the United Nations on OK the th regulation. Substitutes of CFC 113, 11 are dipertahankan (halon 122) and trifenilamin (halon 123), respectively. Formatrecovery (PI. 121) not used independently, but is the source of chemical raw materials. Tetraphthalate (XB. 124) is used as refrigerant and blowing agent when receiving, for example, polyurethane foam.

Freon General formula C2F1+NCl4-NH are substances with the lowest values of the potential destruction of the ozone layer (SDT). Because SDT PI. II is taken as I, for compounds of General formula C2F1+NCl4-NH values of the potential destruction of the ozone layer does not exceed 0.02. In modern chemical technology freon 121 and 122 receive from perchloroethylene and hydrogen fluoride in the liquid phase using patalastas antimony as a catalyst (1). The process is carried out at 150aboutWith the catalyst charge in the amount of 6 wt. from the supplied perchlorethylene, the contact time of the reactants 3 h, the molar ratio of the supplied hydrogen fluoride to the perchlorethylene is 2.5. The yield of halon 121 35% halon 122 54% Lack of process is the low yield. The authors are not known liquid-phase methods of obtaining halon 124. The most restim hydrogen in the presence of petaluridae antimony as a catalyst (2). Charged to the reactor petaluridae antimony and put her fluoridation first at 60aboutWith further rise of temperature up to 130aboutC. total for the two temperature exposures supply hydrogen fluoride is 10 moles per mole patalastas antimony. Next continuously at 130aboutWith the reactor serves halon 122 and hydrogen fluoride in a molar ratio of 1:1. The degree of conversion of halon 122 43% yield PI. 123 38% of the content products 5% selectivity to 88.4%

When conducting similar conditions fluoridation halon 121 the degree of conversion of CHL. 121 85% yield of HFC 123 29% of the content of undesirable isomer of HFC 123 (1,1,2-Cryptor-1,2-dichloroethane) get in the way of CHL. 123 1%

The disadvantages of the prototype are:

use as feedstock partially fluorinated compounds, halocarbons-121, 122, derived from perchloroethylene or trichloroethylene;

low technological parameters of the process, when used as a feedstock halon 122, the degree of transformation of raw materials does not exceed 43% and the yield of the desired product 38%

Thus when using antimonic catalyst process is carried out in two stages. At first srdanov-121 and 122 synthesize HFC-123.

The invention is directed to a process in one stage, increasing the degree of conversion of raw materials and increase the yield of target products.

The task is achieved by the fact that as the catalyst used petaluridae antimony with modifying additive tin tetrachloride, and the modifying additive is taken in the ratio 13-60 molar percent to patalastas the antimony and the catalyst is subjected to preliminary treatment with hydrogen fluoride at a molar ratio of 1:(6-16) at a temperature of 20-150aboutC and a pressure of 0.1 to 2.3 MPa.

When the process is loaded into the reactor petaluridae antimony and tin tetrachloride containing the latter 13-60% compared to patalastas antimony treated with hydrogen fluoride at a ratio of 6 to 16 moles of hydrogen fluoride per one mol of the catalyst is calculated based on the molar fractions of downloadable patalastas antimony and tin tetrachloride, at a temperature of 20-150aboutC and a pressure of 0.1 to 2.3 MPa, and then continuously served perchloroethylene, or trichloroethylene and hydrogen fluoride in a molar ratio of 3-10 at a temperature synthesis 110-150aboutWith the pressures of 0.1 to 2.3 MPa. Synthesis products continuously turn is of perchloroethylene or trichloroethylene hydrogen fluoride in the presence of a catalyst, composed of a mixture of chlorides of tetravalent tin and pentavalent antimony. Thus, the authors claim that the claimed method meets the requirements of novelty. In addition, the authors found that in the present conditions, the interaction of perchloroethylene and hydrogen fluoride in the presence of pure tin tetrachloride is missing (example 1).

The process of liquid-phase fluorination in the presence as catalyst patalastas antimony containing 13-60% tin tetrachloride allows to increase the yield of the target product and to increase the selectivity of the process. So comparable to prototype conditions (example 2) when fluoridation halon 122 output of HFC-123 increased from 38 to 44.6% of the content of the undesired isomer 1,1,2-Cryptor-1,2-dichloroethane is 0.7%, the content of by-products is reduced from 5 to 1.4% and the selectivity of the process of fluorination increases with 88,4 to 94.9% In the compared objects fusion temperature is equal to the prototype 130aboutSince, in the present invention 120aboutC. the Molar ratio of hydrogen fluoride per mole of catalyst at the stage of preliminary fluorination in the prototype 10, and the proposed method is 8.75.

The same is achieved a higher yield of the target product and a reduced content of impurities, i.e., increases the selectivity of the process.

In table. 1 shows the dependence of the degree of conversion of perchloroethylene and exit halon 122 from the catalyst composition.

The content of tin tetrachloride less than 13% is not advisable, because it does not change the output halon 122, and the content of tin tetrachloride above 60% leads to a decrease in the output of halon 122. The maximum yield of halon 122 is achieved at equimolar ratio of tin tetrachloride and petaluridae antimony.

The authors found that the yield of the target product affected by pre-treatment of the catalyst is hydrogen fluoride, namely when the molar ratio of hydrogen fluoride to the catalyst equal to 1:(6-16). The increase in this ratio from 8.75 (example 2) to 14.6 (example 3) leads to an increase in the degree of conversion of halon 122 with 47,0 to 62.7% and the yield of HFC-123 from 44.6 to 61,1, the selectivity of the process with 94,9 to 97.5%

The degree of conversion of halon 122 and the output of HFC-123 on the molar ratio of hydrogen fluoride to the catalyst are presented in table. 2, when 50% of the content of tin tetrachloride, 120aboutAnd duration of the synthesis of 2,5 hours

From the data table. 2 shows that when the molar ratio feliciana ratio above 16 does not change the performance of the process, thus the valid interval of the change of molar ratio is equal to from 6.0-16.0.

On the claimed catalyst is effective fluorination of perchloroethylene and trichloroethylene in one stage to CFC-122, 123, and halon 122 to 123. So when 130aboutWith 51.5% of the content of tin tetrachloride in patalastas antimony, a molar ratio of hydrogen fluoride to pray catalyst is 8.75, contact time of 5 h the full extent of the transformation, for example, perchloroethylene, the output of halon 122 accounts for 74.7% of HFC-123 13,7% (example 4).

With increasing molar ratio of hydrogen fluoride to pray catalyst to 15.6 output of HFC-123 is increased to 21.2% (example 5).

The process of fluorination of perchloroethylene or trichloroethylene in the presence of antimony-olivanova catalyst is carried out at a temperature of 110-150aboutWith better 120-130aboutC. If the temperature drops below 110aboutWith considerable speed slow process, when the temperature rises above 150aboutWith a decrease in the selectivity of the process due to the occurrence of adverse reactions of synthesis products.

Halon 121 obtained by using as feedstock perchloro - etileno raw materials of perchloroethylene (examples 2, 3, 5). In the above example 3, the content of halon 124 in the products of synthesis is equal to 2.1 per cent higher than when using traditional antimonic catalyst. This allows the selection of halon 124 as a commercial product.

The process is carried out at a pressure of 0.1 to 2.3 MPa, better than the 0.2-1.5 MPa. The increase in pressure (above 2.3 MPa) requires a temperature rise in the reactor, namely above 150aboutWith that will lead to reduced yield of the target products and the decrease in selectivity. At pressures below 0.1 MPa decreases the speed of the process.

Thus, these positive results in the implementation of the proposed method, namely the process in one stage, increasing the degree of conversion of the feedstock, increase the yield of target products, can only be achieved by a combination of the following characteristics:

use as catalyst patalastas antimony containing 13-60 mol. tetrachloride of tin;

the use of pre-treatment of the catalyst is hydrogen fluoride at a molar ratio of 1: (6-16) at a temperature of 20-150aboutC and a pressure of 0.1 to 2.3 MPa.

Based on the above, the authors argue that the claimed method meets the requirement "and the

P R I m e R 1. In a reactor with a volume of 0.18 DM3download 0,34 mole of tin tetrachloride and 0.78 mol of perchloroethylene. Heat the contents to 155aboutWith and within 2 hours serves 3 mol of hydrogen fluoride. The pressure in the reactor support of 0.62 MPa. The contents of the reactor dissolved in the cooled concentrated hydrochloric acid. The organic layer is separated from the catalyst, washed and dried by silicagel. The organic phase analyzed chromatographically. Get to 0.78 mol of perchloroethylene.

P R I m m e R 2. In a reactor with a volume of 0.18 DM3reverse water-fridge and a throttling valve load of 0.23 mol patalastas antimony and 0.25 mole of tin tetrachloride. A reactor equipped with a jacket for heating its fluid silicone oil and a pocket for thermocouples. At room temperature for one hour serves 2 mol of hydrogen fluoride at a pressure in the reactor of 0.2-0.3 MPa. The temperature in the reactor was raised to 120aboutWith simultaneous supply of 2.2 moles of hydrogen fluoride, pressure support 1.5 MPa. Then quickly fed into the reactor to 0.55 mol of halon 122, pressure support 1.8 MPa, and for 2.5 h serves to 2.5 mol of hydrogen fluoride. With the gradual reduction of pressure to atmospheric Oh layer was washed with hydrochloric acid, water and dried over silicagel. The composition of organic products determine chromatography. Get: Halon 122 53,0% HFC-123 43,86% HFC-123 SIMM. 0.7% HFC-124 1.0% Halon -112 0,047% Halon 113 1,3% other 0,093%

P R I m e R 3. Conditions similar to example 2 except that at room temperature the catalyst serves to 2.5 mol of hydrogen fluoride and when the temperature of the reaction mixture to 120aboutWith additional 4.5 mol of hydrogen fluoride. Get: Halon 122 35.2% Halon 122 SIMM. 0.05% HFC-123 60,4% HFC-123 SIMM. 0,70% HFC-124 2.10% Halon 112 0.05% Halon 113 1,4% other 0,1%

P R I m e R 4. In a reactor with a volume of 0.28 DM3(the design of the reactor is similar to example 1) load of 0.32 mol patalastas antimony and 0.34 mole of tin tetrachloride (51 mol.). At room temperature for one hour serves 2 mol of hydrogen fluoride. The pressure in the reactor support 0,5-0,8 MPa. The temperature in the reactor was raised to 120aboutWith simultaneous supply of 3 moles of hydrogen fluoride. Then quickly fed into the reactor to 0.8 mole of perchloroethylene. The temperature in the reactor support 130aboutWith the pressure of 1.7 MPa for 5 h serves to 5.2 mol of hydrogen fluoride. Get: HFC-124 0,30% HFC-123 12.4% Of the HFC-123 SIMM. 1,38% Halon 122 74,70% Halon 122 with patalastas antimony and 0.25 mole of tin tetrachloride (52% mole.). At room temperature for 0.5 h serves 1.0 mol of hydrogen fluoride. The pressure in the reactor support of 0.5 MPa. The temperature in the reactor was raised to 120aboutWith simultaneous supply of 6.0 moles of hydrogen fluoride. The pressure support 1.5 MPa. Then quickly fed into the reactor to 0.6 mole of perchloroethylene, pressure support 1.5 to 1.8 MPa and within 9 h serves 6,55 of moles of hydrogen fluoride. Get: Halon 122 71,1% Halon 122 SIMM. 0.04% HFC-123 20.1% Of the HFC-123 SIMM. 1,11% HFC-124 1.0% Halon 112 0,55% Halon 113 1,73% HFC-114 0.02% Perchlorethylene 3,3%

P R I m e R 6. In the reactor of 200 DM3download 25 mole patalastas antimony and 26 mole of tin tetrachloride (50 mol.). At room temperature serves 100 moles of hydrogen fluoride. The pressure in the reactor support of 0.5 MPa. The temperature in the reactor was raised to 120aboutWith simultaneous supply of 660 moles of hydrogen fluoride. The pressure support of 1.4 MPa. Next continuously served for 286 h 345 kg trichloroethylene, 313 kg of hydrogen fluoride and 199 kg of chlorine. Get: Halon 122 51,08% HFC-123 5,79% Halon 113 15,44% Halon 133 7,49% HFC-132 17,16% Trichloroethylene totaling 3.04%

P R I m e R 7. Conditions similar to example 4 except that the temperature in the reactor support 120< Halon 122 SIMM. OTS. The halon 121 61.4 per cent of the Halon 112 4,0% Halon 113 1,1%

P R I m e R 8. Conditions similar to example 6 except that continuously serves hydrogen fluoride is two times smaller, namely 156 kg. Get: Halon 121 55,0% Halon 122 9.4% Of the HFC-123 2.3% Of the Halon 113 10.5% Halon 133 4.6% HFC-132 14.7% Trichloroethylene 3,5%

P R I m e R 9. Conditions similar to example 5 except that the temperature in the reactor was raised to 150aboutC. Receive: Halon 122 30.0 Halon 122 SIMM. OTS. Refrigerant-123 51,9 Refrigerant-123 SIMM. 1.5 HFC-124 15,5 Halon 112 0.1 Halon 113 0.5 Halon 114 1,0 Perchlorethylene 0,5

1. The METHOD of producing GLODEANU General formula C2Fn+1Cl4-nH, where n 0 3, the interaction of the corresponding halogeton or kaleidotile with hydrogen fluoride in the liquid phase at elevated temperature in the presence of a catalyst pretreated hydrogen fluoride patalastas antimony, characterized in that the use of catalyst containing 13 additional 60 mol. tetrachloride of tin, and the processing of the catalyst is carried out at a molar ratio of hydrogen fluoride and catalyst 6 16 1 and the process is conducted at a temperature rising from 20 to 150oC and a pressure of 0.1 to 2.3 MPa.

2. The way portalatin.

3. The method according to PP.1 to 3, characterized in that in the case of perchloroethylene interaction with hydrogen fluoride is carried out at a temperature of 120 - 150oC and a pressure of 0.2 to 2.3 MPa.

4. The method according to PP. 1 and 2, characterized in that in the case of trichloroethylene interaction with hydrogen fluoride is carried out in the presence of chlorine at a temperature of 120 150oC and a pressure of 0.2 to 2.3 MPa.

5. The method according to p. 1, characterized in that in the case of dipertahankan interaction with hydrogen fluoride is carried out at a temperature of 120 - 150oC and a pressure of 0.2 to 2.3 MPa.

 

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