The method of obtaining monomers


(57) Abstract:

Usage: raw material for various FERPLAST. The inventive obtaining vinyl fluoride, 1,1-defloration, triptorelin lead thermal dehydrocorydaline fluorinated Atanov in the reactor from hromonikelevoj alloy, pre-processing of the inner surface of the products of pyrolysis in the presence of water vapor, when the ratio of the source Atanov to couple 2 3 1, at 650 To 700C, followed by pyrolysis at 700 To 900C, contact time of 0.05 to 2.5 C. table 4.

The invention relates to the production of fluorine-containing monomers, namely the synthesis of vinyl fluoride, 1,1-defloration and triptorelin used as feedstock to produce different grades of fluoropolymers.

One of the main methods of producing vinyl fluoride (PV) is the catalytic hydroperiodide acetylene. As the catalyst used lF3[1] Al2ABOUT3coated with Tio2, d or Cd(F4)2[2] NH4.FF [3] Zn3, CRF3, uF3[4] the oxide of Zn and CD deposited on activated carbon [5] mercury salts on coals [6] etc., Other methods of obtaining the PV based on K(PI. 152) at a temperature of 250-350aboutWith the pressures of 0.1-10 MPa on fluorinated Al2ABOUT3with the addition of salts of manganese (conversion of CHL. 152 82.7% of the output of an 80.2%) [7] on Al2ABOUT3with palladium (yield 73%) [8] or dehydrochlorination by pyrolysis of 1,1-perchlorate at 500-800oWith the pressure of 5-500 mm RT. Art. contact time of 0.1-10 in the presence of nitrogen or carbon dioxide (conversion of 91% selectivity 95%) [9] or in the presence of a catalyst (copper and copper salt) [10] the dehydrochlorination of 1-fluoro-2-chlorethane in the presence of a catalyst and without it [11]

Of the following methods to obtain the PV of the most promising for industrial implementation is its reception by dehydrohalogenating perchloromethyl of Atanov as the production of PV-based catalytic gidroftorirovaniya acetylene, has some significant drawbacks: limited time of operation of the catalyst, the complexity of creating a reactor of large capacity due to the high exothermic effect of the reaction and the explosiveness of the production facility.

Method of generating PV dehydrohalogenating haloesters of Atanov the most promising is a pyrolytic method dehydrocorydaline 1,1-differetn (PI. 152), which refers C in the patent literature are not described.

In the patent literature reflects many different ways to obtain 1,1-defloration (TEU), but of particular interest pyrolytic methods of obtaining dehydrohalogenating perchloromethyl of Atanov, for example 1,1-debtor-1-chlorethane (PI.142), and 1,1,1-triptorelin.

We and abroad TEU in the industry is produced by pyrolysis of incubation.142 high selectivity 90-92% conversion of halon 90-95% However, upon receipt of the PI.142 as a by-product formed by chemiluminescence.143, which can be separated by distillation with a purity of 99.95 per cent in sufficient quantities for industrial production TEU its pyrolysis. Besides holdem. 143 is the ozone destruction, the production of which can be arranged.

Different ways of obtaining 1,1-defloration of 1,1,1-triptorelin is described in detail in the patent and journal literature.

Pyrolysis 1,1,1-triptorelin carried out in a platinum or platinum lined reactors at a temperature of 820aboutC and a contact time of 0.2 s [12, 13] at high temperatures (1050-1500)aboutWith small contact times (0,001-3.0) with at conversion 75-76% and selectivity 98-99% [31] Researchers of the Japanese firm Asahi Garasu showed that prolly at 950aboutWith contact times of 0.36 with selectivity for 1,1-defloration reached 97% conversion of halon 94%

In the above-described methods, the pyrolysis is carried out in platinum reactors and high temperature, which is undesirable in an industrial environment from the point of view of corrosion in the environment of HF. Therefore, the researchers of the company Stauffer Chemical Co did a great job on lowering the temperature pyrolysis due to the use of catalysts, such as Al2ABOUT3, Tio2, PIO, Zn, a mixture of Al2ABOUT3and SIO, SIS2[14] in the presence of ammonium fluoride [15] the Selectivity for 1,1-defloration low and may not be of interest to industrial implementation.

One of the main methods of obtaining triptorelin (TPV), described in the patent literature, is dehalogenase of kalogeropoulou zinc in the environment of the polar organic solvent [16] and hydrogenation of halogenoalkanes and alkenes on the catalyst at elevated temperatures [17] the Disadvantage of the first method is the large number of waste products in the form of solutions Zn2(X=CL, Br), which have virtually no consumers, and the second low duration of operation of the catalyst and a low yield of the monomer (16%) yersterday alkanes. For example TPV can be obtained by pyrolysis of a mixture of diperchlorate (PI.22) and perchloromethane (PI. 31) in a molar ratio of 1:1 at 800aboutWith contact times 1,08-1,14 C. the contents of the TPV is present in the reaction gases amounted to 18.7% molar. When the pyrolysis mixture with a molar ratio of CHL.22/PI.31=10/1, the conversion rate is 26.4% output TPV reacted on PI.31 was $ 70.7% [47]

The main product of the pyrolysis of 1,1,1,2-Tetrafluoroethane (PI.134) when the temperature 1170-1300 is To TPV [19] This work is devoted to kinetic studies of thermal decomposition, i.e., pyrolysis of a mixture containing 1% CR. 134 and 99% argon, in the interval 1170-11410 To increase conversion rates from 0.1-46% To a temperature of 1300 To the main product of pyrolysis is a TPV, and at temperatures above 1300 K, the selectivity decreases due to the formation of impurities of CH3F, F3WITH2HF5WITH2F6C2H3F2F4.

As described pyrolytic methods of obtaining monomers of the General formula C2FxH4-xthermal dehydrocorydaline fluorinated Atanov closest in essence to the proposed object is [13] which describes the pyrolysis of HFC 143 in platinum reactor, when tempera is that selected for the prototype. Despite the high conversion and selectivity of this method, the use of expensive platinum reactor and unaccounted for authors the impact of black carbon during pyrolysis, which in the long run will be irreversibly to sit on the surface of the reactor, causing the formation of by-products, creating a complex obstacle to the creation of industrial production TEU.

The task of the invention is the development of technology for production of monomers of the General formula C2FxH4-xof ozone-fluorinated halocarbons, the production of which is created on an industrial scale.

This object is achieved in that the fluorine-containing atany (freon 152, 143, 134) is subjected to pyrolysis in the reactor from chromium-Nickel alloy with a ratio of surface to volume is not more than 10 cm-1the inner surface of which is pre-treated products of pyrolysis in the presence of steam at a ratio of organic fraction to a couple of 2-3:1, for 20-24 hours at 650-700aboutWith a contact time of 5-10 s, followed by pyrolysis at 700-990aboutWith contact times of 0.05-2,50 C.

The use of steam as a diluent, increasing the selective behaviour and scientific literature does not describe the process of thermal dehydrocorydaline fluorinated Atanov in the presence of water vapor, obviously because of the high corrosivity of HF in the presence of moisture, even in relation to platinum at elevated temperatures.

The authors first studied the process of thermal dehydrocorydaline in the presence of water vapor; investigated the formation of impurities in the system and the corrosive effects of hydrogen fluoride in the presence of water vapor at elevated temperatures of pyrolysis.

It is known [22] to improve the corrosion resistance of some metals is the passivation of the walls of the reactor in the presence of water vapor. For example, the addition of 30% water vapor to Cl2effectively inhibits the corrosion of aluminium, iron and its alloys; corrosion rate of copper and lead is not dependent on the presence of water vapor in the atmosphere of chlorine, while the corrosion of Nickel is accelerated.

The authors have shown that the process of thermal dehydrocorydaline alkanes can be carried out in reactors of the available and cheap chrome-Nickel alloy, for example HNT, in the presence of water vapor after passivation of the walls of the reactor of pyrolysis products of pyrolysis and steam under certain conditions. When passivation is formed HF and water vapor is formed on the surface of the dense semitically water vapor decrease of the ratio of the surface of the pyrolysis reactor to its volume S/V reduces the amount of by-products (CO and H2in pyrolysate.

The combination of these features, namely, carrying out the pyrolysis of fluorinated Atanov in the presence of superheated water vapour, taken in a specific molar ratio, in chromium-Nickel reactor with a certain ratio S/V, under certain time and temperature conditions and the application of the passivation reactor products of pyrolysis and steam will allow to create industrial production of valuable fluorine-containing monomers of the General formula C2FxH4-xthat will be characterized by a high selectivity for deep conversion of the feedstock.

To study the pyrolysis of fluorinated Atanov (PI.152, 134, 143) in the presence of water vapor was established laboratory setting, allowing you to identify the patterns of process and optimal technological parameters. Pyrolysis of HFC 152 in the presence of water vapor was tested on the pilot plant.

The pyrolysis reactor was a tube made of chromium-Nickel alloy HN78T, which are made from industrial pyrolysis reactor, the length of 980 mm, diameter 4 mm, temperature Measurements in the reactor were carried out using thermocouples; temperature difference along the length of the isothermal part the T-3 with an accuracy of 1aboutC.

Superheated steam received dosing distilled water from the tank by a pump dispenser "Lew" and filed in the evaporator, then in the superheater, where steam overheated up to 850-950aboutC.

Refrigerant from the cylinder was fed to the heater, where it is heated to 400-500aboutC.

Heated to the specified temperature refrigerant and the vapor was fed to the heated up to 750-900aboutWith the pyrolysis reactor. Dosing of halon and the pair was performed automatically and managed computers.

Coming out of the reactor, the gas-vapor mixture was cooled quenching the refrigerator up to 150-200aboutWith and received in the condenser-collector hydrofluoric acid formed by condensation of water vapor and absorption of HF from pyrolysate. The capacitor made of the f-4 was cooled refrigerator coil placed inside.

The gas phase after collector acid was subjected to neutralization, drying and condensation.

The resulting pyrolyzate analyzed using gas-liquid chromatography on device d Tgaag-570 using a flame ionization detector with a carrier gas helium at a column filled with 15% tricresylphosphate-80 (fraction of 0.16-0.2 mm).

To study the corrosion resistance, it is Aya was a tube of alloy HN78T diameter x mm, length 300 mm, filled with samples of various materials, which are continuously filed pairs, inert and HF in a ratio close to the real part of pyrolysate.

To study the effect of the surface of the reactor selectivity of the process of thermal decomposition of HFC 152 in the presence of water vapor and to study the process of passivation of the walls of the reactor of pyrolysis was created in the workshop of the experimental setup, similar to the laboratory, but the length of the reactor was 3.2 m, a diameter of 8 mm was acquired experimental party F-CH2and sent for testing in ONPO Plastpolymer.

In table. 1,2,3 examples pyrolysis halocarbons 152, 143, 134, respectively.

From table.1 shows that the pyrolysis of HFC 152 conduct below 700about(Example 1) is impractical due to the low conversion of the feedstock, and above 900about(Example 13) due to the lower selectivity of the process PE.

Examples 4-7 illustrate the influence of the degree of dilution of HFC 152 water vapor: when it is increased, increasing the concentration of CO and H2in pyrolysate; when the molar ratio of steam to halon equal 1 (example 6) and H2a little, but there is the appearance of soot. Conducting pyrolysis at contact times of less than 0.05 with impractical due to low is Ty PE (less 82,24%).

Experiments (example 15-19) show that the pyrolysis PI.-152 in the reactor, which S/V is less than 2 times than that of the reactor laboratory setup, passes with greater selectivity for PV by reducing the CO and H2in pyrolysate.

It should be noted that in the transition from experimental reactor to industrial, from whom S/V not more than 0.4-0.8 cm-1the amount of CO and H2plummet and selectivity will increase to 90-96%

Examples 20 and 21 illustrate the role of passivation reactor products of pyrolysis at 700aboutWith contact times of 5 s and in the presence of water vapour, taken in a molar ratio to the HFC 152 is equal to 2-3 for 24 hours Without passivation selectivity decreased from 96.6 percent to 87,05%

In table.2 illustrates the pyrolysis of HFC 143 in the presence of water vapor and the optimal process conditions. It is seen that to pyrolysis at the time of contact is below 0.05 s and a temperature of at least 800aboutSince it is impractical due to the low conversion of raw materials (examples 1.8) and above 0.5 (example 5) due to the lower selectivity of the process for 1,1-defloration.

Also determined that the optimal pyrolysis temperature of 900aboutC, because at higher temperatures decreases the selectivity prey increase increases the formation of CO and H2while lower observed the appearance of soot.

Carrying out the pyrolysis in the reactor nozzle, S/V which is 6.5 times higher (example 10) showed that the selectivity decreased to 88%

Example 11 shows the deterioration process of conversion and selectivity during pyrolysis in the reactor without prior passivation products of pyrolysis in the presence of water vapor.

In table.3 shows the experimental results obtained in a laboratory setup for the pyrolysis of HFC 134 in the presence of water vapor in the temperature range of 800-900aboutC.

From experiments 1,2,8,9 shows that to pyrolysis at 800aboutSince it is impractical due to the low conversion of HFC 134, and at 900aboutWith due to the low selectivity of the process on the monomer. The experiences of 2.9 illustrate the impact of dilution steam: when the degree of dilution of the above 3 decreases the selectivity of the process by increasing the CO and H3. The most favorable temperature for carrying out the pyrolysis temperature is 850aboutWith dilution water vapor is equal to 2. However, at high contact time (op.7: 4) decreases the selectivity of the process for triptorelin.

Pyrolysis of HFC 125 not researched the industry is inappropriate. There is a cheap industrial method of obtaining this monomer of halon 22. The authors carried out one experience that showed the possibility of formation of tetrafluoroethylene in the pyrolysis of HFC 125 in the above formula the temperature and time settings.

In table. 4 presents data for the study of corrosive HF in the presence of water vapor. In an environment of dry hydrogen fluoride in stationary conditions (examples 1-4) the best results in corrosion temperature has a chrome-Nickel alloy HN78T, but long-term operation under continuous gas flow formed loose film will deteriorate and volatile salts, included in its composition (NiF3CrF3), will be swept from the surface of the reactor, which will lead to further corrosion.

Examples of 5.6 illustrate the influence of water vapor on the corrosion activity of the chromium-Nickel alloy. Example 6 shows that the long-term test at a temperature of pyrolysis formed of a dense film of PIO, Nir3and spinel reduces the corrosion rate on the order; in the examples of 7.8 shows that after passivation reactor corrosion rate of chromium-Nickel alloy is reduced.

It is established that formed whim hydrogen fluoride, forming volatile salts of Nickel and chromium (CRF3, NiF3).

The influence of water vapor on the rate of corrosion of other metals (12X18H10T, senior 3, Al and so on) has not been studied, as already at 300-520aboutWith these alloys have high corrosion rate and the temperature of pyrolysis is much higher (700-900aboutC).

Thus, the data obtained by the pyrolysis of freon 152, 143, 134 show that you can organize industrial production of obtaining vinyl fluoride, vinylidene and triptorelin, which will be characterized by a high selectivity with respect to the monomer (90-93%) conversion of the feedstock (70-80%).

The METHOD of OBTAINING MONOMERS of General formula


where 1 x 3,

thermal dehydrocorydaline fluorinated Atanov in a metal reactor, characterized in that use reactor made of chromium-Nickel alloy with respect to its surface-to-volume not more than 10 cm-1the inner surface of which is pre-treated products of pyrolysis in the presence of water vapor, at a molar ratio of the source Atanov to pair 1:(2-3) for 20-24 h at a temperature of 650-700oC, contact time of 5-10 s, followed by the feast of the Sabbath.


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FIELD: chemistry.

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EFFECT: improved action of the catalyst.

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