CN209885775U - Device for preparing 1,1,1, 3-tetrachloropropane - Google Patents
Device for preparing 1,1,1, 3-tetrachloropropane Download PDFInfo
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- CN209885775U CN209885775U CN201920281839.5U CN201920281839U CN209885775U CN 209885775 U CN209885775 U CN 209885775U CN 201920281839 U CN201920281839 U CN 201920281839U CN 209885775 U CN209885775 U CN 209885775U
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Abstract
The utility model discloses a prepare 1,1,1, 3-tetrachloropropane's reaction unit, including reation kettle, reation kettle sets up the ethylene circulation system outward, and gas distributor is established to the reation kettle bottom, and the ethylene circulation system is including establishing the ethylene extraction pipe on reation kettle upper portion, establishing ethylene impressed pipe, the ethylene compressor of establishing between ethylene extraction pipe and impressed pipe in the reation kettle lower part, ethylene impressed pipe and gas distributor intercommunication. The utility model reduces the generation amount of the gum oil-shaped by-product in the process of preparing 1,1,1, 3-tetrachloropropane by reacting carbon tetrachloride with ethylene through arranging the ethylene circulating system outside the reaction kettle, and improves the selectivity of the main product 1,1,1, 3-tetrachloropropane; the utility model discloses reation kettle among the device does not need agitating unit, has reduced the pressure of ethylene in the reation kettle under close reaction rate.
Description
Technical Field
The utility model relates to an organic halide preparation field especially prepares device of 1,1,1, 3-tetrachloropropane.
Background
1,1,1, 3-tetrachloropropane is a key raw material for synthesizing trichloropropene and trifluoropropene, and can be used as a paint remover, a degreasing agent and a solvent. The synthesis method of 1,1,1, 3-tetrachloropropane mainly comprises a peroxide method (CA691213A), an electromagnetic radiation method (CA807638A), a metal complex and a cocatalyst method, wherein the peroxide method and the electromagnetic radiation method are not suitable for industrial production due to low synthesis efficiency or harsh reaction conditions, the metal complex and the cocatalyst method are suitable for industrialization due to mild reaction conditions and high synthesis efficiency, but inevitably generated colloid oil substances are adhered to the inner wall of a reaction kettle and a stirring device, and are very unfavorable for long-term continuous production.
US4605802A discloses a method for preparing 1,1,1, 3-tetrachloropropane by reacting carbon tetrachloride and ethylene, wherein the catalyst is phosphite ester and iron powder, preferably ferric chloride is additionally added, the reaction is carried out for 5.5-22.6 hours at 95 ℃ and 758kPa, the conversion rate is 45-88.5%, and the selectivity is 94.9-96.3%. The iron powder is left in the reactor after the reaction is finished and is used for the next reaction; preferably, the reactor is washed with a solvent such as dichloromethane or acetone before the next reaction.
CN106146247A discloses adding carbon tetrachloride, tributyl phosphate and ferrous chloride into a catalyst preparation tank, and stirring uniformly to obtain a uniform mixture, wherein the molar ratio of each component in the mixture is as follows: adding the prepared uniform mixture into an autoclave with stirring through a metering pump, maintaining the reaction temperature at 90 ℃, continuously introducing ethylene to maintain the reaction pressure at 1.1MPa, keeping the reaction time for 1h, continuously extracting a reaction crude product, and performing chromatographic analysis, CCl4The conversion rate was 80%, and the product 1,1,1, 3-tetrakisThe selectivity to chloropropane was 93%.
JP2017137263A discloses that a metal complex catalyst is dissolved in a liquid phase, ethylene and carbon tetrachloride are subjected to an addition reaction to obtain a reaction liquid containing 1,1,1, 3-tetrachloropropane, the reaction liquid is subjected to high-speed centrifugal separation to produce a phase separation, and the metal complex catalyst is in a light phase and the 1,1,1, 3-tetrachloropropane is in a heavy phase. The separation of the catalyst ensures that the reaction product does not generate side reaction in the distillation process, thereby ensuring the high purity of the reaction product. Reacting 0.55mol iron and 0.1mol dimethylacetamide relative to 100mol carbon tetrachloride at 130 deg.C and 0.6MPa while continuously adding dimethylacetamide for 2.5hr until the total amount is 0.636mol, and continuing reaction for 5hr, CCl4The conversion was 94% and the product selectivity 98%.
The prior art improves the conversion rate of raw materials, the selectivity of products and the operability of a device through catalyst improvement and post-treatment process change, but does not fundamentally solve the problem of generating a colloidal oily substance in the reaction.
SUMMERY OF THE UTILITY MODEL
To the problem that the in-process of prior art carbon tetrachloride and ethylene reaction preparation 1,1,1, 3-tetrachloropropane generated gluey oiliness thing, the utility model discloses an improve the device that carbon tetrachloride and ethylene reaction preparation 1,1,1, 3-tetrachloropropane, reation kettle peripheral hardware ethylene circulation system has reduced gluey oiliness thing yield.
The reaction formula for preparing 1,1,1, 3-tetrachloropropane by reacting carbon tetrachloride with ethylene is as follows:
since ethylene is easily polymerized at high temperature and high pressure, in addition to the above main reaction, there are also a series of side reactions, which produce gum oil-like by-products:
in the same catalyst, excessive ethylene or higher ethylene concentration is the main cause of side reaction, and the reduction of ethylene concentration or ethylene pressure in the reaction system is the key to reduce the side reaction.
The utility model provides a device for preparing 1,1,1, 3-tetrachloropropane by reacting carbon tetrachloride and ethylene, which comprises a reaction kettle, wherein an ethylene circulating system is arranged outside the reaction kettle, a gas distributor is arranged at the bottom in the reaction kettle, the ethylene circulating system comprises an ethylene extraction pipe arranged at the upper part of the reaction kettle, an ethylene press-in pipe arranged at the lower part of the reaction kettle, and an ethylene compressor arranged between the ethylene extraction pipe and the press-in pipe, and the ethylene press-in pipe is communicated with the gas distributor; the reaction kettle is also provided with carbon tetrachloride, a catalyst feeding port and a reaction liquid discharging port; and an ethylene feed inlet is arranged on the ethylene extraction pipe.
Preferably, the length-diameter ratio of the reaction kettle is 1.5-60, and further preferably 2-15; the too little fat type reation kettle of slenderness ratio, gas-liquid phase contact time is short, is unfavorable for the gas-liquid reaction, otherwise, too big slenderness ratio, and the bubble takes place the gathering at long distance rising in-process, makes the gas-liquid area of contact reduce, has reduced reaction efficiency.
Preferably, the gas distributor is made of sintered metal porous materials, and further preferably, the gas distributor is a sintered metal porous screen plate, the area of the screen plate is 30-90% of the cross section area of the reaction kettle, so that the uniform distribution of gas is ensured, and reaction liquid can be sufficiently circulated in the reaction kettle;
the reaction kettle can fully stir the liquid phase through the ethylene bubbling from the gas distributor without an additional stirring device, can avoid the safety risk caused by the high-speed dynamic friction of the stirring device, can also avoid the collision of the metal catalyst and the reaction kettle wall caused by stirring, and greatly reduces the manufacturing cost of the reaction kettle.
Preferably, the ethylene compressor is an oil-free compressor, so as to prevent lubricating oil from causing adverse effects on the reaction; the pressure difference between the exhaust port and the air suction port of the ethylene compressor is 0.1-3.0 MPa, and the exhaust volume is 0.4-18 Nm/cubic meter of the volume of the reaction kettle3Min; the ethylene compressor only needs to provide pressure for overcoming the liquid level difference in the reaction kettle to enable the ethylene to circulate in the reaction kettle, and the required powerAre small; the discharge capacity of the ethylene compressor is the expression of the ethylene circulation capacity, too small a discharge capacity cannot provide enough ethylene to contact and react with the liquid phase, and too large a discharge capacity causes excessive boiling of the liquid phase, so that the reaction system is unstable.
The external ethylene circulating system ensures that ethylene is fully exchanged between a gas phase and a liquid phase, and even if the ethylene pressure in the reaction kettle is lower, the ethylene amount dissolved into the reaction liquid or contacted with the reaction liquid can be ensured, thereby ensuring the smooth reaction of carbon tetrachloride and ethylene.
The process for preparing 1,1,1, 3-tetrachloropropane by using the reaction device comprises the following steps: firstly discharging air from a reaction kettle, then adding a catalyst and carbon tetrachloride, introducing ethylene, starting an ethylene compressor, pumping the ethylene out of the upper part of the reaction kettle, pressurizing the ethylene by the ethylene compressor, pressing the ethylene into the reaction kettle from the lower part of the reaction kettle, distributing the ethylene pressed into the reaction kettle by a gas distributor, then introducing the ethylene into a reaction system, controlling the ethylene pressure in the reaction kettle to be 0.15-0.50 MPa, heating to 80-130 ℃ for reaction, and stopping the reaction when the conversion rate of the carbon tetrachloride in a reaction solution is 60-85%.
The catalyst is conventional carbon tetrachloride and ethylene telomerization catalyst. The catalyst can be selected from ferric chloride, ferrous chloride, cuprous chloride, etc., and the cocatalyst can be selected from tripropyl phosphite, tributyl phosphite, etc.
Compared with the prior art, the utility model has the advantages of as follows:
1. an ethylene circulating system is arranged outside the reaction kettle, so that the generation amount of a gum oil-like byproduct in the process of preparing 1,1,1, 3-tetrachloropropane by reacting carbon tetrachloride and ethylene is reduced, and the selectivity of a main product 1,1,1, 3-tetrachloropropane is improved;
2. the utility model discloses a reation kettle among the reaction unit of preparation 1,1,1, 3-tetrachloropropane does not need agitating unit, has reduced the pressure of ethylene in the reation kettle under close reaction rate.
Drawings
FIG. 1 is a schematic structural diagram of the apparatus for preparing 1,1,1, 3-tetrachloropropane according to the present invention.
In figure 1,1 is a reaction kettle, 2 is carbon tetrachloride and a catalyst charging port, 3 is an ethylene extraction pipe, 4 is an ethylene charging port, 5 is an ethylene compressor, 6 is an ethylene pressing pipe, 7 is a discharging port, and 8 is a gas distributor
Detailed Description
As shown in figure 1, the device for preparing 1,1,1, 3-tetrachloropropane comprises a reaction kettle, wherein an ethylene circulating system is arranged outside the reaction kettle, and a gas distributor is arranged at the bottom of the reaction kettle; the ethylene circulating system comprises an ethylene extraction pipe 3 arranged at the upper part of the reaction kettle 1, an ethylene press-in pipe 6 arranged at the lower part of the reaction kettle 1, and an ethylene compressor 5 arranged between the ethylene extraction pipe 3 and the press-in pipe 6, wherein the ethylene press-in pipe is communicated with a gas distributor 8; the upper part of the reaction kettle is provided with a carbon tetrachloride and catalyst feed inlet 2, the lower part of the reaction kettle is provided with a reaction liquid discharge port 7, and an ethylene draw-out pipe is provided with an ethylene feed inlet 4; the reactor is made of stainless steel, the gas distributor is a multi-layer sintered metal mesh plate, the average pore diameter is 0.3-50 mu m, the porosity is 25% -45%, the area of the gas distributor is 30% -90% of the cross section area of the reactor, the ethylene compressor is an oil-free ethylene compressor, and the pressure difference between an exhaust port and an air inlet is 0.1-3.0 MPa.
The reaction device is adopted below, and specific parameters and use conditions of the present invention are further illustrated by combining with the embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
A 5000L reaction kettle made of stainless steel has a length-diameter ratio of 3, discharges air, adds 5kg of catalyst ferric chloride, 32kg of reduced iron powder, 25kg of cocatalyst tributyl phosphite and 3750kg of carbon tetrachloride, and leads ethylene to enter from an ethylene charging port, so that the ethylene pressure in the reaction kettle reaches 0.20 MPa; starting the oil-free ethylene compressor, the pressure difference between the exhaust port and the air inlet is less than or equal to 1.2MPa, and the exhaust volume of the ethylene compressor is 17.5Nm3Min, pumping ethylene out of the upper part of the reaction kettle, pressurizing the ethylene by an ethylene compressor, pressing the ethylene into the reaction kettle from the lower part of the reaction kettle, and distributing the ethylene pressed into the reaction kettle into a reaction system by a gas distributor, wherein the gas distributor is a multi-layer sintered metal mesh plate, the average pore diameter is 0.45 mu m, the porosity is 38 percent, and the gas is gasThe area of the distributor is 65 percent of the cross section area of the reaction kettle; heating to 95 ℃ for reaction, supplementing ethylene, controlling the pressure of the ethylene in the reaction kettle to be 0.18-0.22 MPa, reacting for 7.5 hours, sampling for gas chromatographic analysis, wherein the conversion rate of 1,1,1, 3-tetrachloropropane is 73.4 percent, the selectivity of 1,1,1, 3-tetrachloropropane is 99.5 percent, and the reaction is stopped, and the secondary addition by-product is 0.4 percent, 1,1, 3-tetrachloropropane is 76.2 percent, carbon tetrachloride is 23.4 percent, and the secondary addition by-product is 0.4 percent.
Example 2
The ethylene pressure in the reaction kettle is controlled to be 0.46-0.50 MPa, other steps are the same as those in example 1, and gas chromatography analysis is performed on a sample, wherein 85.4% of 1,1,1, 3-tetrachloropropane, 13.9% of carbon tetrachloride, 0.7% of secondary addition by-products, 84.0% of conversion rate of reduced carbon tetrachloride and 99.3% of selectivity of 1,1,1, 3-tetrachloropropane are obtained.
Comparative example 1
The reaction kettle is not provided with an ethylene circulating system, reaction liquid is stirred by a mechanical stirring device, the ethylene pressure in the reaction kettle is controlled to be 0.78-0.82 MPa, the reaction time is 11 hours, other steps are the same as those in the embodiment 1, samples are taken for gas chromatography, and 75.9% of 1,1,1, 3-tetrachloropropane, 21.2% of carbon tetrachloride, 2.4% of secondary addition byproducts and other 0.5% are obtained, the conversion rate of the tetrachloro carbon is 79.0%, and the selectivity of the 1,1,1, 3-tetrachloropropane is 96.3%.
Claims (7)
1. The device for preparing the 1,1,1, 3-tetrachloropropane comprises a reaction kettle and is characterized in that an ethylene circulating system is arranged outside the reaction kettle, a gas distributor is arranged at the bottom in the reaction kettle, the ethylene circulating system comprises an ethylene extracting pipe arranged at the upper part of the reaction kettle, an ethylene pressing pipe arranged at the lower part of the reaction kettle, and an ethylene compressor arranged between the ethylene extracting pipe and the ethylene pressing pipe, and the ethylene pressing pipe is communicated with the gas distributor.
2. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 1, wherein the length-diameter ratio of the reaction kettle is 1.5-60.
3. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 2, wherein the length-diameter ratio of the reaction kettle is 2-15.
4. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 1, wherein the gas distributor is made of sintered metal porous material.
5. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 1, wherein the gas distributor is a sintered metal porous mesh plate, and the area of the mesh plate is 30-90% of the internal cross-sectional area of the reaction vessel.
6. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 1, wherein the ethylene compressor is an oil-free compressor.
7. The apparatus for preparing 1,1,1, 3-tetrachloropropane according to claim 1 or 6, wherein the pressure difference between the exhaust port and the suction port of the ethylene compressor is 0.1-3.0 MPa, and the exhaust amount is 0.4-18 Nm/m of the volume of the reaction kettle3/min。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111659322A (en) * | 2019-03-06 | 2020-09-15 | 浙江佳汇新材料有限公司 | Device and process for preparing 1,1,1, 3-tetrachloropropane |
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