The method of liquid-phase chlorination of butadiene
(57) Abstract:The invention relates to organic synthesis, in particular, to obtain a mixture WITH4chlorohydrocarbons predecessors jordanovic monomers for the synthesis of rubber. The main products in the mixture are 3,4-dichlorobutene-1,1,4-dichlorobutene-1, three - and tetrachlorobutane. Continuous liquid-phase chlorination of butadiene lead by conducting the reaction at boiling of the reaction mixture in the environment ethyl chloride containing 6 to 9 wt.% products of the chlorination of butadiene. The process is carried out either without a catalyst or with the use as catalyst of nitrogen-containing compounds, at a temperature of 14 - 30oC, when the molar ratio of butadiene : chlorine = 1.2 to 3 : 1. The catalyst is prepared by adding trialkylamine dissolved in ethyl chloride, the products of the chlorination of butadiene pre-or directly in the implementation process of the reaction. This results in a simpler technology and increases the yield of the final products. 2 C.p. f-crystals. The invention relates to organic synthesis, and in particular, to the improvement of the method of liquid-phase chlorination of butadiene.The products of the chlorination of butadiene are intermediate in the village of malament - and ozone-resistant, high resistance to aging, which is ensured by the presence in the polymer chain of the chlorine atom in a-position to the double bond. In this regard, all Jordanova hydrocarbons are particularly valuable.The known method of chlorination of butadiene-1,3 liquid-phase chlorination of butadiene-1,3 (1) with chlorine in a solvent (CCI4, CHCl3, di-, tri - and tetrachlorethane, C4H8Cl2C6H6, PhCl, PhNO2C6H11C7H16, cyclohexane and so on) in the presence of 0.1-5% (by weight of the solvent sulphur or substances containing sulphur (CS2, Na2S, CaS, Na2S2O3H2, thiophene, mercaptans)) at a temperature of from 20 to 50oC, is obtained without high-boiling impurities dichlorobutene, yield 90% /Japan patent 19564, 1967/.The disadvantage of this method is:
- the use of high-boiling solvents, the allocation of which at elevated temperatures leads to the formation of resinous products, polluting the distillation trichlorobutene and tetrachlorobutane that can be used to obtain valuable dichlorobutane;
- the complexity of the used catalytic systems.Also known is a method of obtaining dichlorobutene by the chlorination of butadiene chlorine in prisutstvie the adiabatic mode at a molar ratio of butadiene and chlorine 1-3 : 1, and carbon tetrachloride take in quantity 4-8 mol per 1 mol of butadiene.The disadvantage of this method is the use of high-boiling solvent, as well as strict temperature conditions for the reaction /patent of USSR 1022960, 1983/.There is also known a method of liquid-phase chlorination of 1,3-butadiene from a mixture of 3,4-dichlorobutene - 1 and TRANS - 1,4-dichlorobutene - 2, comprising contacting 1,3-butadiene and elemental chlorine in a solvent, in an atmosphere essentially devoid of oxygen, in the presence of a chlorination catalyst, at 25-100oC and at a pressure sufficient to provide the resulting reaction mixture boiling point not lower than about 25-100oC when the mass ratio of the solvent and dichlorobutene 2.5 to 100 : 1, the separation of unreacted 1,3-butadiene and solvent from dichlorobutenes and removing dichlorobutenes, and the chlorination is performed in a cooled evaporation reactor, and the solvent is selected from the group consisting of butane, pentane or fluorinated hydrocarbons of the General formula
< / BR>where
R is independently hydrogen, fluorine, chlorine or bromine;
R' is hydrogen;
R" is independently fluorine, chlorine or bromine;
m and n = 0 - 3.The pace is our 1,3-butadiene and the solvent is returned to the reactor.The disadvantage of this method is to conduct the chlorination under pressure, which significantly complicates the technological process /patent of Russia 2051892, 10.01.96/.The closest and declared to the technical essence and the achieved effect is the chlorination of butadiene under isothermal conditions at a temperature of 40-60oC and a pressure of 4-5 bar, using as a low-boiling solvents such as butane, pentane, POLYHALOGENATED formula where R = H; R", R' is F, Cl, Br, m, and n = 0-3, end group, CH3or trihalomethyl.As catalysts for use trialkylamine or phosphines, diallylsulfide or trialkylsilyl chloride in the amount of 20-200 million-1. For inhibition of radical processes apply tert-butylpyrocatechol, phenyl-naphtylamine, fentazin or sulfur to the amount of 20-80 million-1. Ratio of 3.4 : 1,4 HCD: the solvent is 1:2 - 11 /better 1:3 - 6/. The reaction is as follows. In cylindrical Nickel reactor with a height of 23 cm and a diameter of 1.8 cm skip a continuous flow of Cl2with a speed of 0.17 g/C and a mixture of butadiene (0.21 g/s) F2ClCCClF2(the boiling point of the 4oC, the molar ratio of butadiene : chlorine is 1 - 4 : 1) add a solution of phenyl -- and 4.5 ATM, selecting from the cube to the distillation of a mixture of butadiene, 3,4, and 1.4 dichlorobutene (DHB), the solvent and the formed products deeper chlorination.The composition of the distillate:
CIS - 1 wt.%
Trichlorobutene - 1.9 wt.%
Tetrachlorobutane - 4.2 wt.%
Monochlorotoluene - 0.5 wt.%
The disadvantage of this method is the use of fairly complex catalytic systems, complex technological performance of the equipment /U.S. patent 5077443, 1991/.Carrying out the process at elevated temperature and pressure with the use of gaseous solvents and reagents in fact requires the same equipment as in gas-phase chlorination of butadiene.The disadvantage is the use of ozone-dangerous freons, which according to the Montreal agreement on the protection of the ozone layer of the Earth is not recommended for commercial use.The aim of the invention is the improvement of the method of liquid-phase chlorination of butadiene by conducting the reaction at boiling of the reaction mixture in the environment ethyl chloride containing 6-9% of the products of the chlorination of butadiene at a temperature of 14-30oC (advantages is risotti nitrogen-containing compounds mainly trialkyl-1-harbutt-2-yl-ammonium chloride or critically ammonium chloride with o chlorinated products of butadiene from a cube reactor without ethyl chloride or the content of 30-50% by the products of the chlorination of butadiene.The method consists in the following. In a tubular reactor filled with a nozzle, placed ethyl chloride containing 6-9% of the products of the chlorination of butadiene, and in the lower part of the reactor served estimated number of butadiene and chlorine. Boiling ethyl chloride (18-22)oC with unreacted butadiene (the process is conducted at full depletion of chlorine fed to the adsorber with an alkaline reagent and then cooled in a brine refrigerator and a collector, where the pump-dispenser chilled ethyl chloride with dissolved butadiene returned to the middle part of the reactor. The accumulation in the reactor products of the chlorination of butadiene more than 9% they spontaneously gather in the lower part of the reactor, where no ethyl chloride, or with a small amount directed to the collection. In the absence of a catalyst outlet dichlorobutenes, when the molar ratio of butadiene : chlorine equal to 2:1, is 70-75% (the ratio of 3,4-DHB:1,4-DHB = 1:1), the rest of trichlorobutene and tetrachlorobutane. In the presence of 0.005 to 0.05% (mainly 0,008%) to chloride ethyl trialkyl-1-harbutt-2-yl-ammonium chloride, obtained by adding the corresponding trialkylamines in the products of the chlorination of butadiene, or critically ammonium harm-ethyl, the return of the cooled collection in the reactor.The developed technology of liquid-phase chlorination of butadiene in comparison with the Prototype and other cited works has the following advantages:
simple technological process, under mild reaction conditions and obtain the desired products without solvent or with a small content;
- use as a low-boiling solvent (boiling point of 12.8oC), legkorastvorimah ethyl chloride, which is ozone friendly product;
- the use of catalysts, synthesized from the products of chlorination of butadiene (mainly of 1,4-dichlorobutene-2) adding to the mixture of the products of the chlorination of butadiene relevant trialkylamines that does not require installation of special site preparation of catalysts;
- the possibility of obtaining products of the chlorination of butadiene in a wide range of selectivity, providing high output dichlorobutenes and trichloroethanol and tetrachlorobutane predecessors remote 2,3-dichlorobutadiene;
- low consumption of the process.The method is illustrated in the following primeralinea nozzle and is equipped with three nozzles in the lower part of the reactor (low to output products of the chlorination of butadiene, the average for the supply of butadiene, and the third is located 2 cm above the average for entering chlorine) and fitting in the middle part of the reactor to enter recirculated ethyl chloride, is placed 75 grams of ethyl chloride containing 0,008 wt.% triethyl-1-harbutt-2-yl - ammonium chloride or critically ammonium chloride.Then in the corresponding fitting serves 0,624 g/min of styrene and 0.273 g/min of chlorine (the molar ratio of butadiene : chlorine is 3 : 1). The temperature in the reactor rises to 18-20oC and ethyl chloride, wikipedi from the upper part of the reactor together with unreacted butadiene, through the nozzle head is sent to the absorber filled with crystalline NaOH, and then goes in the fridge cooled brine.Condensed ethyl chloride together with dissolved butadiene is collected in a cooled receiver, where the pump is dosing the mixture is fed into the middle portion of the reactor. Previously in the receiver dissolve 0,008 wt.% to ethyl chloride catalyst. Sustainable mode of chlorination occurs after 15-20 minutes, when ethyl chloride is accumulated 6-9 wt.% products of the chlorination of butadiene, and they spontaneously begin to accumulate at the bottom of the reactor, where in composition:
1. 3,4 - DHB - 69 wt.%
2. TRANS.-1,4-DHB - 18 wt.%
3. CIS -. -1,4-DHB - 3 wt.%
4. Trichlorobutene to 3.8 wt.%
5. Tetrachlorobutane - 5.4 wt.%
6. Monochlorotoluene to 0.8 wt.%.Example 2.In the conditions of example No. 1 of the chlorination was carried out in the absence of catalyst, feeding butadiene speed 0,436 g/min, chlorine 0,196 g/min Obtained 100 g of a mixture of chlorination products of composition:
1. 3,4 - DHB - 36 wt.%
2. TRANS.-1,4-DHB - 34 wt.%
3. CIS -. -1,4-DHB - 1.4 wt.%
4. Trichlorobutene - 9.2 wt.%
5. Tetrachlorobutane - 18 wt.%
6. Monochlorotoluene - 1.4 wt.%.Example 3
In the conditions of example No. 2, the accumulation of chloride in the ethyl 6-9% of the products of the chlorination of butadiene, together with recycled ethyl chloride in the reactor serves triethylamine in an amount of 0.1% to the solvent. After the chlorination process (1-1 .5 hours) on a sustainable mode of supply of butadiene and chlorine increase accordingly to 0,624 g/min and 0.273 g/min, respectively. For 5 hours the reactor was obtained 120 g of a mixture of products of composition:
1. 3,4 - DHB - 68 wt.%
2. TRANS.-1,4-DHB - 20 wt.%
3. CIS -. -1,4-DHB - 3 wt.%
4. Trichlorobutene - 3 wt.%
5. Tetrachlorobutane - 6 wt.%
6. Monochlorotoluene - 1 wt.%.Example 4
you're reactor received 132 g of a mixture of products of composition:
1. 3,4 - DHB - 62 wt.%
2. TRANS.-1,4-DHB - 25 wt.%
3. CIS -. -1,4-DHB - 1 wt.%
4. Trichlorobutene - 5.1 wt.%
5. Tetrachlorobutane - 6.2 wt.%
6. Monochlorotoluene - 0.7 wt.%.Example N 5
In the conditions of example No. 1 molar ratio supplied butadiene and chlorine is 1.2:1 at a feed rate 0.124 g/min and 0,136 g/min, respectively. 5 hours of reactor operation received 71 g of a mixture of the composition:
1. 3,4 - DHB - 57 wt.%
2. TRANS.-1,4-DHB - 26 wt.%
3. CIS -. -1,4-DHB - 2 wt.%
4. Trichlorobutene - 2.8 wt.%
5. Tetrachlorobutane - 12 wt.%
6. Monochlorotoluene - 0.2 wt.%
Example N 7
In the conditions of example No. 1, the number of triethyl-1-harbutt-2-yl-ammonium chloride ranges from 0.005% to ethyl chloride.For 5 hours received 104 g of a mixture of products of composition:
1. 3,4 - DHB - 45 wt.%
2. TRANS.-1,4-DHB is 30.5 wt.%
3. CIS -. -1,4-DHB - 1.5 wt.%
4. Trichlorobutene - 6 wt.%
5. Tetrachlorobutane - 16 wt.%
6. Monochlorotoluene - 1 wt.%
Example N 8
In 500 g of ethyl chloride was added 0.08 g of triethylamine and 0.06 g of allyl chloride. The mixture was stirred for at least 1 hour and used as a solvent chlorination of butadiene under the conditions of example No. 1.5 hours of reactor operation received 131 g dichlormethane - 3 wt.%
5. Tetrachlorobutane - 6 wt.%
6. Monochlorotoluene - 1 wt.%. 1. The method of liquid-phase chlorination of butadiene chlorine in halodurans solvent at boiling of the reaction mixture, wherein the process is conducted in an environment ethyl chloride containing 6 to 9 wt.%, mainly 7 wt.%, products of the chlorination of butadiene at a temperature of 14 - 30oC, mostly 18 - 22oC, when the molar ratio of butadiene : chlorine, equal to 1.2 - 3 : 1, and the process is conducted recycle ethyl chloride, with the output products of the chlorination of butadiene from a cube reactor in the absence of ethyl chloride or content of 30 to 50 wt.%.2. The method according to p. 1, wherein the process is conducted in the presence of nitrogen-containing catalyst selected from triethyl - or tributyl-1-harbutt-2-yl-ammonium chloride or critically ammonium chloride, taken in an amount of 0.005 to 0.05 wt.% in the calculation of the chloride ethyl, mainly in the number 0,008 wt.%.3. The method according to p. 2, characterized in that the catalyst is obtained by adding the products of the chlorination of butadiene, composed mainly of 1,4-dichlorobutene-2, or allyl chloride dissolved in ethyl chloride, the corresponding three is
FIELD: industrial organic synthesis.
SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.
EFFECT: reduced expenses due to using production waste.
4 tbl, 30 ex
FIELD: petrochemical and industrial organic synthesis.
SUBSTANCE: process comprises separating gaseous pyrolysis products to recover ethylene-containing fraction with 54-65% ethylene content and C3-C5-hydrocarbon fraction. Ethylene-containing fraction is subjected to liquid-phase catalytic chlorination. Gas phase of chlorination product is purified via adsorption and fed into furnace as fuel. C3-C5-Hydrocarbon fraction is subjected to exhaustive hydrogenation, hydrogenation product is combined with fresh raw material at weight ratio (0.05ч1):1 and sent to pyrolysis plant.
EFFECT: achieved integration of process, increased reliability thereof, and reduced expenses.
1 dwg, 1 tbl, 15 ex
FIELD: organic chemistry.
SUBSTANCE: 1,2-dichloroethane is obtained by liquid phase ethylene chlorination with discharging of reaction heat due to operation medium boiling. In claimed process nitrogen is added to chlorine and ethylene reagents. Ratio of chlorine volume consumption to nitrogen volume consumption is maintained as 1:1. Reaction is carried out at temperature lower than 1,2-dichloroethane boiling point, and discharging of reaction heat is carried out by evaporative cooling of operation medium in nitrogen.
EFFECT: process of increased selectivity; decreased yield of by-products.
1 tbl, 5 dwg
FIELD: chemical industry; designs of the bubble-type reactors for production of 1.2-dichloroethane.
SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
1 ex, 4 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. The process is carried out by direct feeding gaseous reagents chlorine and ethylene in liquid reaction medium of reactor. Before feeding into reactor chlorine and ethylene are heated preliminary in heat-exchangers to temperature equal to that of liquid in reactor. Method provides enhancing selectivity of process and reducing formation of by-side substances representing higher chlorine-derivatives of ethane.
EFFECT: improved method of synthesis.
4 dwg, 1 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. Method involves maintaining the optimal ratio of heat eliminated based on evaporation and heat eliminated based on cooling a liquid medium in a heat exchanger in the process. One-sixth part of heat formed in reactor is eliminated based on evaporation of synthesized compound in boiling and 5/6 part of formed heat is eliminated based on circulation of liquid working medium in external heat exchanger. The temperature gradient in the reaction zone is maintained equal 52°C. Invention provides enhancing selectivity of process and reducing amount of by-side products of reaction (higher chlorine-derivate of ethane).
EFFECT: improved method of synthesis.
3 dwg, 1 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to a process of liquid-phase chlorination of ethylene wherein reaction heat is removed by means of vaporization of reaction medium. Process is conducted at vacuum-mediated reduction of reaction medium boiling temperature below 60°C, vacuum being developed because of condensation of vapors formed in external condenser accompanied by removal of non-condensed gases by vacuum pump.
EFFECT: enhanced selectivity of process and decreased yield of by-products (higher chlorine derivatives of ethane).
FIELD: chemical industry.
SUBSTANCE: vacuum reactor comprises tower (1), distributors of chlorine (2) and ethylene (3), circulation pipe (5), perforated plates (6), condenser (7), pump (8), vacuum-pump (9), and hydraulic valve (10).
EFFECT: improved quality of the product.
FIELD: chemical industry; apparatuses for production of the chlorinated allyl.
SUBSTANCE: the invention presents the reactor for production of the chlorinated allyl intended for realization of the method of production of the chlorinated allyl by the direct gaseous phase chlorination of the propylene. The reactor includes the closed circuit of circulation of the reaction gases, the devices of injection of the source propylene and chlorine, the device of the forced circulation of the part of the reaction gases and the device of withdrawal of the other part of the reaction gases. At that the closed circuit of the reaction gases circulation forms the jet pump, which includes in series connected the reception chamber, the mixing chamber and the diffuser, and the pipe of the circulation circuit connecting the outlet of the diffuser with the appropriate inlet of the reception chamber of the injector and acting as the main reaction zone of the ideal displacement with the presence time of 0.7-0.9 s, in which the scatter of the temperatures does not exceed ±10°С. The reception chamber contains the nozzles used as the devices for injection of the source propylene and chlorine. The jet pump ensures fulfillment of the concerted functions: introduction of the streams of the source propylene and chlorine, which are the working injecting streams; the forced circulation pump with the repetition factor of 5-10 of the reaction gases stream, which is the injected stream; the high-velocity mixer and the preheater of the source reactants in the mixing chamber due to the strong turbulence during (0.01-0.04)s, which is formed by the combination of the nozzles of the injected gases at the arrangement of the nozzle/ nozzles of the chlorine coaxially to the main nozzle of the propylene arranged on the shaft of the mixing chamber. The technical result of the invention is, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
EFFECT: the invention provides, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
1 ex, 1 dwg