The way to obtain 1-fluoro-1,1-dichloroethane, 1,1-debtor-1 - chlorethane, 1,1,1-triptorelin and the reaction device node for its implementation

 

(57) Abstract:

The invention relates to a method for producing 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin. The process of interaction of organochlorine compounds with hydrogen fluoride is carried out at elevated temperature and pressure followed by separation of the desired products. Moreover, the source of organochlorine compound 1,1-dichlorethylene or 1,1,1-trichloroethane served under a layer of liquid hydrogen fluoride at a molar ratio of the source of hydrogen fluoride and a source of organochlorine raw 1,0 - 1,1 : 1,0. The interaction was carried out under continuous circulation of hydrogen fluoride in a closed process loop at a temperature and pressure equal to the equilibrium pressure of hydrogen fluoride at this temperature. The reaction mixture is distilled off from the circulating hydrogen fluoride, condense, and then hydrogen fluoride in the form of phlegmy with a reflux ratio of 2 to 5 return on interaction. Hydrogen chloride is directed to the obtaining of hydrochloric acid, and condensed target products separate, purify and produce. A device for implementing the process includes a reactor volume type distillation column, the condenser base is wrapped loop. The result reduces the loss of hydrogen fluoride and reduced formation of by-products. 2 S. and 3 C.p. f-crystals, 1 tab., 2 Il.

The invention relates to the field of chemical technology, namely the production of 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin.

1-Fluoro-1,1-dichloroethane is a low-toxicity solvent and can be used as a foaming agent, 1,1-debtor-1-chlorate and 1,1,1-trifluoroethane are refrigerants and feedstock for other fluorinated compounds.

1-Fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorate and 1,1,1-trifluoroethane receive a liquid-phase method of 1,1,1-trichloroethane (methyl chloroform) or 1,1-dichlorethylene (vinylidenechloride) and hydrogen fluoride in the presence of a catalyst or non-catalytic manner. As a catalyst hydroperiodide 1,1-dichlorethylene use the tin tetrachloride is used (Patent UK N 627773, class C 07 C 17/00, published. 16.08.1949 g), antimony halides (U.S. Patent N 2146354, class C 07 C 19/08, published. 1940), the halides of tantalum. As catalysts exchange fluorination of 1,1,1-trichloroethane use the halides of antimony (U.S. Patent N 2146354, CL, C 07 C 19/08, published. 1940), tin tetrachloride (Patent UK N 627773, class C 07 C 17/the Oia 1,1-debtor-1-chlorethane of 1,1-dichlorethylene.

Known methods of liquid-phase non-catalytic obtain 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorate and 1,1,1-triptorelin of 1,1,1-trichloroethane (U.S. Patent N 3833676, class C 07 C, 17/20, published. 03.09.1974, European application N 0407689, class C 07 C 19/08, published. 15.07.1989,) and 1,1-dichlorethylene (Patent Canada N 2004831, class C 07 C 19/08, published. 1991).

All the above processes are carried out by feeding hydrogen fluoride in the reactor volumetric type, filled with a catalyst in a mixture of chloro-organic raw (or one of organochlorine raw material in the case of a non-catalytic process), with vesennih temperature and pressure. The specified level in the reactor is maintained by feeding into the reactor a source of organochlorine raw materials.

In European patent application N 0402626 (class C 07 C 19/08, published. 15.07.1989 g) the device is non-catalytic site of synthesis (Fig.1) fluorination of 1,1,1-trichloroethane in which the reactor volume type 10 is connected with a distillation column 16. The selection of fusion products for subsequent separation is performed in the gas phase after planted dephlegmator 18 column 16. The molar ratio fed to the reactor, the source of hydrogen fluoride to 1,1,1-trichloroethane is 3,0 - 5,2; reflux the number returned from delegat is 7 - for 27.2 wt.% hydrogen fluoride, which is separately allocated from the reaction mixture and returned to the synthesis. This solution scheme of the reaction site does not allow you to fully condense organic products and hydrogen fluoride, which complicates further processing.

The main disadvantage of these processes is the formation of significant quantities of resinous products due to the propensity of 1,1,1-trichloroethane and 1,1-dichlorethylene to spontaneous oxidation and polymerization, in the presence of metal salts of Lewis acids, which are used catalysts are the halides of tin, antimony, tantalum, or when touching the source of organochlorine raw material of the walls of the reactor and the products of corrosion of the equipment under non-catalytic process. Thus, according to (Patent Canada N 2004831, class C 07 C 19/08, published. 1991), the content of resinous substances in the products of synthesis reaches 15 %. All this leads to deactivation of the catalyst and need frequent replacement in the case of a catalytic process or accumulation of resin in the reactor volume during non-catalytic process.

All these processes are carried out with considerable contact time, reaching several caseria, what causes the technological stage of selection of unreacted hydrogen fluoride and an extra node dosing return of hydrogen fluoride at the site of synthesis, which is associated with the inevitable loss products at these stages.

Closest to the claimed method is a method (international application WO 091/18852, class C 07 C 19/08, published. 12.12.1991,) (prototype) to obtain 1-fluoro-1,1-dichloroethane from 1,1-dichloroethylene and hydrogen fluoride non-catalytic manner. The original 1,1-dichloroethylene and hydrogen fluoride are loaded into the reactor, the process is carried out periodically at temperatures of 75 - 125oC, double molar excess of hydrogen fluoride to 1,1-dichlorethylene compared with the stoichiometry and time contacy 2.5 to 5 hours. The products of reaction is distilled off from the reactor, neutralized and analyzed.

The total conversion of the original 1,1-dichlorethylene 99,3 98,7% formed: at the 75oC was 86.7%, 100oC - 83,2% and 125oC - 79% 1-fluoro-1,1-dichloroethane, to 16% (at a temperature of 125oC) 1,1-debtor-1-chlorethane and up to 3-4% 1,1,1-triptorelin. In the products of synthesis remains to 1.3% unreacted source 1,1-dichlorethylene and also contains up to 4.7% of oligomer products of polymerization of IP is of type serves hydrogen fluoride and 1,1-dichlorethylene at a temperature of 120oC, a pressure of 18 bar (18 kgf/cm2and a molar ratio of hydrogen fluoride to 1,1-dichlorethylene equal to 1.7. The content of the target product - 1-fluoro-1,1-dichloroethane is 91,2%.

The disadvantages of the prototype are:

- the insufficient sensitivity of the process to increase the reaction temperature; when the temperature increases from 75 to 125oC the output of one of the most important products of the synthesis of 1,1-debtor-1-chlorethane increases from 4 to 16%, the yield of 1,1,1-triptorelin remains almost constant;

the process is conducted at a substantial excess of hydrogen fluoride, so the excess hydrogen fluoride is necessary to allocate and make dosing return of hydrogen fluoride in the form of a separate stage of the process, which complicates the process and increases the loss of hydrogen fluoride;

- the presence in the products of synthesis resins and oligomers, resulting in additional stages of separation of the products of synthesis, loss of raw materials - 1,1-dichlorethylene and the emergence of unusable waste production;

incomplete conversion of 1,1-chlorethylene, resulting in a complicated purification process 1-fluoro-1,1-dichloroethane due to proximity to its boiling point (31,9oC) and the temperature is 25oC), which leads to unnecessary energy consumption.

Object of the invention is:

- development of technological process of joint obtain 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin with adjustable these products depending on the needs of and device schematic of the reaction site, which allows this process;

- reduction of losses of hydrogen fluoride by reducing excess hydrogen fluoride fed to the reactor, in relation to the original organochlorine raw materials and by eliminating a separate stage dosing return hydrogen fluoride;

- reduce the formation of oligomers and resins, thereby reducing losses to the original 1,1-dichlorethylene or 1,1,1-trichloroethane and reducing the number of unusable waste production;

- reducing energy consumption by reducing the temperature of the process;

- increase the conversion of 1,1-dichlorethylene or 1,1,1-trichloroethane, reducing the amount of unreacted 1,1 - dichlorethylene products synthesis and thereby simplifying cleaning method 1-fluoro-1,1-dichloroethane from impurities 1,1-dichlorethylene.

This object is achieved by those who (Fig.2), consisting of reactor volume type with a distillation column, condenser, gazorazdelitel (rasseivatelja two immiscible liquid phases), in which a continuous circulation of hydrogen fluoride in a closed loop: the reactor - column - condenser patristical - column reactor. Dosing the original fororganizing raw - 1,1 - dichlorethylene or 1,1,1-trichloroethane and hydrogen fluoride (if the ratio is close to stoichiometric) is, in contrast to all previously known methods, in the volume under the layer of liquid hydrogen fluoride, which is in the reactor at the appropriate temperature and this temperature the equilibrium pressure. In reacting due to the large volume, compared to stoichiometry, excess hydrogen fluoride, there is a very rapid interaction of organochlorine raw material with hydrogen fluoride with the formation of the desired products and their distillation from the reactor together with the circulating hydrogen fluoride, without accumulation of organochlorine raw materials and liquid products of the synthesis reactor.

Unlike schematics (European application N 0402626, class C 07 C 19/08, published. 19.12.1990,) (Fig.1), the proposed technological shemale and enter patristical. Full condensation is achieved by the proposed ustroystva reaction site (Fig.2).

The selection of a liquid mixture of 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin is carried out from the lower phase of gazorazdelitel with subsequent supply for phase separation, purification and selection of the finished products. The proposed device the reaction site allows the top layer of gazorazdelitel - hydrogen fluoride is continuously returned into the distillation column in the form of phlegmy. Hydrogen chloride after the condenser comes on stage acquisition of hydrochloric acid.

Compared with the prototype of the proposed method allows the simultaneous reception of 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin in a predetermined ratio with high conversion source organochlorine raw materials, reduction in the formation of resins and oligomers, with a large output at comparable temperatures 1,1-debtor-1-chlorethane and 1,1,1-triptorelin, to reduce the required temperature reactor for pre-emptive obtain 1-fluoro-1,1-dichloroethane, to reduce the loss of hydrogen fluoride. Compared with the prototype by regulating the temperature of the hydrogen fluoride in the reactor and consequently ravnovesie.

Only the simultaneous combination of all the following distinctive characteristics as in the production method, and device reaction node to achieve the above results; such features are:

- the presence of the reactive site consisting of reactor volume type of the column above the reactor, condenser, photoretinitis;

continuous circulation of hydrogen fluoride in the reaction site in a closed con tour: reactor - column - condenser - patristical column reactor;

maintaining the pressure in the reaction node corresponding to the equilibrium pressure of hydrogen fluoride at a given temperature holding process in the reactor;

- feed in a reactor source of organochlorine raw materials (1,1-dichlorethylene, 1,1,1-trichloroethane) and hydrogen fluoride in a ratio close to the stoichiometric, and under a layer of hydrogen fluoride, the filling volume of the reactor;

- selection perchlorobenzene products of synthesis in the liquid phase from the bottom phase of gazorazdelitel.

The use of these signs is only possible together, using each characteristic separately does not lead to the goal. Thus, continuous m that stream is condensed in the condenser product enters patristical, from which the top layer (hydrogen fluoride) is returned to the column as phlegmy, and the bottom layer (perchlorobenzene products) is selected for further processing. In the reaction site is supported by a pressure equal to the equilibrium pressure of hydrogen fluoride at a given temperature in the reactor.

The deviation of the pressure in the reaction site from the equilibrium at a given temperature hydrogen fluoride in the reactor leads to the termination of circulation of hydrogen fluoride - pressure increase leads to the decrease of flow warded off hydrogen fluoride from the reactor, the overflow of the reactor and stop the drain of hydrogen fluoride from gazorazdelitel; the decrease in pressure leads to rapid evaporation of the hydrogen fluoride from the reactor, its devastation, the Gulf of columns and gazorazdelitel:

With this device, and the principles of operation of the reaction site selection of fusion products for further separation and selection of the target products is only possible in the liquid phase from the bottom phase of gazorazdelitel.

Changing the order of presentation of the components in the reactor, namely the supply of hydrogen fluoride in the amount of chlorine the productivity of the reactor due to the inability or difficulty to create sufficient excess hydrogen fluoride in relation to organochlorine raw materials, and leads to rapid resinification of chloro-organic raw (1,1-dichloroethylene, 1,1,1-trichloroethane), the accumulation of resinous products in the reactor and consequently the gradual attenuation of the chemical reaction in the reactor and the circulation of hydrogen fluoride from driving syphon feed.

The filing of the original organochlorine components and hydrogen fluoride in the reactor with a mandatory excess of the stoichiometric ratio of hydrogen fluoride to the source of organochlorine raw materials, but not more than 10 mole. % The increase in this ratio by more than 10% leads to an increase of the level in the reactor, i.e., leads to the accumulation of hydrogen fluoride in the reactor. The decrease in this ratio leads to a reduction in the reactor, i.e., to use hydrogen fluoride from the reactor.

The authors found that the proposed device circulating the reaction site in combination with the feed to the reactor source of organochlorine feedstock and hydrogen fluoride in a ratio close to the stoichiometric, and under a layer of hydrogen fluoride in the reactor, a certain dependence of the temperature and pressure in the reaction site, the selection perchlorobenzene products Sint is 1-fluoro-1,1 - dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin in industrial production.

According to the authors, the totality of such evidence, as the reaction device node, continuous circulation therein of hydrogen fluoride, the supply of raw materials in a ratio close to the stoichiometric, and under a layer of hydrogen fluoride in the reactor, a certain dependence of the temperature in the reactor and the pressure at the site of synthesis and selection perchlorobenzene fusion products in liquid form from gazorazdelitel in the proposed method meets the criterion of "substantial differences".

The specific execution of the process.

The process is worked out on the pilot plant, which confirmed the reproducibility and reliability for each individual product. Below is a method of carrying out the process.

The specific process parameters and the results are shown in the table.

Reactor 1 (Fig.2) 1 liter is filled with hydrogen fluoride. The reactor is heated to a predetermined temperature and when the pressure in the system is equal to the equilibrium pressure of hydrogen fluoride at this temperature, the circulation of hydrogen fluoride in a continuous loop reactor 1 level of hydrogen fluoride in the reactor is brought to 600 cm3. Monitoring the level in the reactor is manufactured by viewing glass with tick marks. Then into the reactor via siphons, lowered to the bottom of the reactor begins dosing pumps source of organochlorine raw - 1,1-dichlorethylene or 1,1,1-trichloroethane at a speed of 100 cm3/h under a layer of hydrogen fluoride, and hydrogen fluoride with a speed of 28 cm3/h (in the case of filing 1,1-dichlorethylene) or 21 cm3/h (in the case of filing 1,1,1-trichloroethane), which is 10 mole. % more than the stoichiometric amount of hydrogen fluoride relative to supplied to the corresponding chlorinated organic raw materials. The duration of each experience - 8 p.m. At the process level in the reactor 1 remains constant - 600 cm3. Formed perchlorobenzene the reaction products after the condensation is collected in patristical 4 (bottom layer), which are selected for further processing and selection the sample for analysis. Hydrogen fluoride from gazorazdelitel as phlegmy with a reflux ratio of 2 to 5 enters the upper part of the column.

At the opening of the reactor after the end of the experience and operaniuni system on the inner surface at the siphons plaque resin was absent.

The process is the same when using the method of the process depends on the temperature in the reactor and the corresponding equilibrium pressure of hydrogen fluoride.

The results of examples shown in the table.

1. The way to obtain 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin interaction of organochlorine compounds with hydrogen fluoride at elevated temperature and pressure followed by separation of the target product, characterized in that the source of organochlorine compound 1,1-dichlorethylene or 1,1,1-trichloroethane served under a layer of liquid hydrogen fluoride at a molar ratio of the source of hydrogen fluoride and a source of organochlorine raw materials to 1.0 - 1.1 : 1.0, and the interaction was carried out under continuous circulation of hydrogen fluoride in a closed process loop at a temperature and pressure equal to the equilibrium pressure of hydrogen fluoride at this temperature, the reaction mixture is distilled off from the circulating hydrogen fluoride, condense, and then hydrogen fluoride in the form of phlegmy with a reflux ratio of 2 to 5 return on interaction, hydrogen chloride is directed to the obtaining of hydrochloric acid, and condensed target products separate, purify and release.

2. The method according to p. 1, characterized in that to obtain 1-fluoro-1,1-dichloroethane interaction is carried out at 63 - 83oC and 4.0 - 7.0 at the s carried out at 120 - 130oC and 16.6 - 20,2 ATA (1,66 - 2,02 MPa).

4. The method according to p. 1, characterized in that to obtain 1,1,1-triptorelin interaction takes place at temperatures over 130oC and a pressure of more 20,2 ATA (2,02 MPa).

5. The device of the reaction site to obtain 1-fluoro-1,1-dichloroethane, 1,1-debtor-1-chlorethane and 1,1,1-triptorelin includes a reactor volumetric type, distillation column, condenser, patristical, characterized in that the reactor volume type connected in series with the rectifying column located at a height above the reactor, which is connected to the capacitor, the bottom of which is connected to fasoracetam, with the upper part of gazorazdelitel connected with the upper part of the distillation column, the lower part of a distillation column connected to the reactor, forming a closed circulation loop, moreover, the lower part of gazorazdelitel connected with system separation and purification of target products, the top part of the capacitor is connected to the purification system of hydrogen chloride and obtain hydrochloric acid.

 

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