CN115245792B - Chloroacetic acid synthesis system and synthesis method - Google Patents
Chloroacetic acid synthesis system and synthesis method Download PDFInfo
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- CN115245792B CN115245792B CN202211155196.2A CN202211155196A CN115245792B CN 115245792 B CN115245792 B CN 115245792B CN 202211155196 A CN202211155196 A CN 202211155196A CN 115245792 B CN115245792 B CN 115245792B
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Abstract
The invention relates to the technical field of chloroacetic acid production, and particularly relates to a chloroacetic acid synthesis system and a synthesis method. In the chloroacetic acid synthesis system, a synthesis reactor comprises a gas-liquid separation section and a synthesis reaction section; the bottom of the synthesis reaction section is provided with a chlorine inlet, and the side wall of the lower end of the synthesis reaction section is provided with a feed liquid inlet; the top of the gas-liquid separation section is provided with a gas phase outlet, and the upper end of the gas-liquid separation section is provided with a liquid outlet overflow port; the gas phase outlet is connected with the tail gas cooler, the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer in sequence, the bottoms of the tail gas cooler, the first-stage vaporizer and the third-stage vaporizer are connected with the feed liquid inlet, and the upper parts of the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer are connected with the chlorine inlet; the overflow port of the discharged liquid is connected with the upper part of the secondary vaporizer. The synthesis reaction section of the invention adopts a long tubular reaction cylinder, gas and liquid phase materials enter from the lower part of the synthesis reactor and flow out from the upper part, the gas and the liquid phases are in full contact without back mixing, and the reaction conversion rate is improved.
Description
Technical Field
The invention relates to the technical field of chloroacetic acid production, and particularly relates to a chloroacetic acid synthesis system and a synthesis method.
Background
Chloroacetic acid is an important chemical raw material, can be used for producing glycine, carboxymethyl cellulose, ethyl chloroacetate and the like, and is also widely applied to the fields of medicines, papermaking, chemicals, plastic processing, auxiliary agent active agents, spice essence and the like.
The industrial chloroacetic acid is prepared by using acetic anhydride as catalyst and chloridizing acetic acid with chlorine. The production process of chloroacetic acid can be divided into a continuous method and a batch method, the batch method is mainly used in the early stage, but the batch method is gradually eliminated in recent years due to small product yield, poor quality and high pollution, and then the process is converted into a continuous method process which is more environment-friendly and has high product quality. The continuous process mainly comprises four steps of chlorination reaction, hydrolysis impurity removal, hydrogenation impurity removal and rectification refining, wherein the chlorination reaction is the core of the whole process.
The existing continuous chlorination reactor is similar to the traditional batch method, all reactors are standard reaction kettles, acetic acid, acetic anhydride and liquid chlorine are respectively introduced into the reactors from the top of the reaction kettle according to a proportion for reaction, a mixed solution containing chloroacetic acid generated in the reaction process enters a subsequent working section for further treatment, the generated hydrogen chloride gas carries liquid phase reaction raw materials and byproducts to be discharged from the top of the reactor, and the hydrogen chloride gas enters a subsequent absorption system after being cooled to remove partial condensate to prepare hydrochloric acid as a byproduct; the heat generated in the reaction process is taken away by circulating water.
The standard kettle type chlorination reactor is widely applied due to simple structure and low cost in small-scale production. With the expansion of production scale, chlorination reactors become a key limiting factor for the overall process. The material back mixing in the standard kettle type chlorination reactor is serious, the material conversion rate in the reactor is reduced, more unreacted materials are brought to the downstream, and the treatment load of the whole downstream system is further increased additionally. In addition, the consumption is increased by cooling the gas phase with a large amount of circulating water, and the hydrogen chloride gas still contains more other materials, so that the material loss is increased, the lost materials finally enter the hydrochloric acid, and the quality of the byproduct hydrochloric acid is also reduced.
Chinese patent CN102274708A discloses an acetic acid chlorination reactor and a reaction process, wherein the acetic acid chlorination reactor is divided into a second (upper) reaction area and a first (lower) reaction area, the two reaction areas are separated by a porous plate, the upper and lower reaction areas can be independently controlled to heat or cool, and the two reaction areas are provided with enough feed inlets or discharge outlets. This patent sets up two reaction zones in a reactor, and liquid is walked from the top down, and gas is walked from the bottom up, makes catalyst concentration, reaction temperature and reaction rate in two reaction zones have the difference through control feeding mode and control reaction temperature to make the chloroacetic acid concentration in two reaction zones have the difference. The main purpose of this patent is to allow complete chlorine conversion.
Chinese patent CN104387258A discloses a chloroacetic acid production method and a chlorination reactor, acetic acid, liquid chlorine and acetic anhydride are mixed in proportion and then enter the chlorination reactor, certain reaction temperature and reaction pressure are maintained, the chlorination reaction is completed in a gravity field of 100-1000 g, and after the reaction is completed, the product is separated and purified according to a continuous production process, and finally the product is obtained. The chlorination reactor comprises a reaction kettle, a supergravity barrel and a driving motor; the inner wall of the reaction kettle is provided with a baffle plate, the top of the reaction kettle is provided with a temperature indicator, a pressure indicator and a safety valve, the top of the reaction kettle is provided with a gas phase outlet, and the bottom of the reaction kettle is provided with a liquid phase outlet; the upper part of the super-gravity barrel is open and is connected with the rotating shaft by two fixed rods; liquid outlet holes are uniformly formed in the side wall; the bottom of the rotary shaft is fixed by a bottom plate, and backflow holes are uniformly distributed; the upper end of the rotating shaft is connected with the driving motor, and the lower end of the rotating shaft is connected with the supporting seat. This patent changes the stirring rake into tubbiness promptly "hypergravity bucket", obtains the hypergravity through high-speed centrifugal pivoted centrifugal force, and high-speed rotation in-process easily produces the friction, and the friction can lead to static gathering, charge discharge again to lead to the flash explosion, there is great potential safety hazard, and the high-speed operation of motor leads to electric energy consumption too big.
Disclosure of Invention
The invention aims to provide a chloroacetic acid synthesis system, which is characterized in that gas-liquid phase materials enter from the lower part and flow out from the upper part, the gas-liquid phase materials are fully contacted, back mixing does not exist, and the reaction conversion rate is improved; the invention also provides a chloroacetic acid synthesis method.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the chloroacetic acid synthesis system comprises a synthesis reactor, a tail gas cooler and a vaporizer, wherein the synthesis reactor comprises a gas-liquid separation section and a synthesis reaction section; the synthesis reaction section adopts a long tubular reaction cylinder, the bottom of the synthesis reaction section is provided with a chlorine inlet, and the side wall of the lower end of the synthesis reaction section is provided with a feed liquid inlet; the top of the gas-liquid separation section is provided with a gas phase outlet, and the upper end of the gas-liquid separation section is provided with a liquid outlet overflow port; the vaporizer comprises a first-stage vaporizer, a second-stage vaporizer and a third-stage vaporizer;
the gas phase outlet is connected with the tail gas cooler, the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer in sequence, the bottoms of the tail gas cooler, the first-stage vaporizer and the third-stage vaporizer are connected with the feed liquid inlet, and the upper parts of the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer are connected with the chlorine inlet; the overflow port of the discharged liquid is connected with the upper part of the secondary vaporizer, and the bottom of the secondary vaporizer is connected with the chloroacetic acid crude product tank.
Wherein:
the feed liquid inlet is connected with a liquid distributor in the synthesis reaction section, and a bubble breaker is also arranged in the synthesis reaction section; one or more bubble breakers are provided.
The length-diameter ratio of the synthesis reaction section is 5-20.
The top of the gas-liquid separation section is also provided with a pressure gauge port, a temperature gauge port, a safety valve port and a liquid level gauge port.
The outer wall of the gas-liquid separation section is provided with a first jacket, the lower end of the first jacket is provided with a first circulating water inlet, and the upper end of the first jacket is provided with a first circulating water outlet; and a second jacket is arranged on the outer wall of the synthesis reaction section, a second circulating water inlet is arranged at the lower end of the second jacket, and a second circulating water outlet is arranged at the upper end of the second jacket. The first jacket and the second jacket are used for removing reaction heat.
The upper part of the tail gas cooler is provided with an anhydride inlet and a circulating water outlet III, and the lower part of the tail gas cooler is provided with a circulating water inlet III and a reaction tail gas inlet; the reaction tail gas inlet is connected with the gas phase outlet.
The upper part of the first-stage vaporizer is provided with a chlorine outlet III, and the lower part of the first-stage vaporizer is provided with a liquid chlorine inlet III and a cooling tail gas inlet; the cooling tail gas inlet is connected with the top of the tail gas cooler, and the chlorine outlet III is connected with the chlorine inlet.
The upper part of the secondary vaporizer is provided with a second chlorine outlet and a feed liquid inlet, and the lower part of the secondary vaporizer is provided with a second liquid chlorine inlet and a first-stage vaporized tail gas inlet; the feed liquid inlet is connected with the discharge liquid overflow port, the chlorine outlet II is connected with the chlorine inlet, and the primary vaporized tail gas inlet is connected with the top of the primary vaporizer.
The upper part of the third-stage vaporizer is provided with an acetic acid inlet and a first chlorine outlet, and the lower part of the third-stage vaporizer is provided with a first liquid chlorine inlet and a second vaporized tail gas inlet; the first chlorine outlet is connected with the chlorine inlet, and the second-stage vaporized tail gas inlet is connected with the top of the second-stage vaporizer.
The top of the three-stage vaporizer is connected with a tail gas treatment device.
The chloroacetic acid synthesis method based on the system comprises the following steps:
(1) Reaction feed liquid enters the synthesis reaction section from a feed liquid inlet at the bottom of the synthesis reaction section and uniformly flows out through a liquid distributor; the chlorine gas is sprayed upwards from a chlorine gas inlet at the bottom of the synthesis reaction section, enters the synthesis reaction section, and is mixed with the reaction feed liquid for chlorination reaction; chlorine and reaction feed liquid flow upwards from the bottom of the synthesis reaction section and pass through a bubble breaker, so that the chlorine and the reaction feed liquid are uniformly contacted and reacted; after the reaction is finished, the material enters a gas-liquid separation section at the upper part, the raw material is fully converted to generate reaction tail gas containing hydrogen chloride, the reaction tail gas enters a tail gas cooler through a top gas phase outlet, and reaction discharge liquid flows out through a feed liquid overflow port; reaction heat generated in the synthesis reactor is taken out by circulating water in the first jacket and the second jacket; the pressure, the temperature and the liquid level in the synthesis reactor are respectively monitored by a pressure gauge port, a temperature gauge port and a pressure gauge, a temperature gauge and a liquid level gauge arranged in the liquid level gauge port;
(2) Reaction tail gas enters the bottom of the tail gas cooler from a reaction tail gas inlet, and is cooled by circulating water, and materials contained in the reaction tail gas are condensed to form condensate; then catalyst acetic anhydride is injected from an acid anhydride inlet at the upper part of the tail gas cooler to further absorb organic matters in the reaction tail gas, and the acetic anhydride is mixed with condensate and flows out from the bottom of the tail gas cooler to be called crude acetic anhydride; the gas phase is discharged from the top of the tail gas cooler and is called cooler tail gas, and the cooler tail gas enters the primary vaporizer;
(3) The tail gas of the cooler enters a primary vaporizer from a cooling tail gas inlet, exchanges heat with liquid chlorine entering from a liquid chlorine inlet III, the liquid chlorine absorbs heat and is vaporized into chlorine gas, so that the organic phase in the tail gas of the cooler is deeply condensed to obtain primary condensate, and the rest tail gas is called primary vaporized tail gas; the first-stage vaporized tail gas is discharged from the top of the first-stage vaporizer;
(4) The first-stage vaporized tail gas enters the second-stage vaporizer from the first-stage vaporized tail gas inlet, the reaction discharge liquid flowing out from the liquid material overflow port enters the second-stage vaporizer from the liquid material inlet and flows down, the first-stage vaporized tail gas blows off hydrogen chloride gas dissolved in the reaction discharge liquid, and the gas phase flows out from the top of the second-stage vaporizer and is called second-stage vaporized tail gas; simultaneously, liquid chlorine is introduced from a second liquid chlorine inlet at the lower part of the secondary vaporizer, and the liquid chlorine absorbs the heat of the reaction discharge liquid to be vaporized to form chlorine; the reaction discharge liquid flows out from the bottom of the secondary vaporizer after being cooled and stripped, and enters a chloroacetic acid crude product tank as a crude product, and is further subjected to deepening treatment in a subsequent working section;
(5) The second-stage vaporized tail gas enters the third-stage vaporizer from the second-stage vaporized tail gas inlet and exchanges heat with the liquid chlorine entering the first liquid chlorine inlet, the liquid chlorine absorbs heat and is vaporized into chlorine gas, the second-stage vaporized tail gas is deeply condensed, the raw material acetic acid is injected and leached from the acetic acid inlet at the upper part of the third-stage vaporizer, and after organic matters in the second-stage vaporized tail gas are further absorbed, crude acetic acid liquid is formed; the treated tail gas flows out from the top of the three-stage vaporizer and is called as three-stage vaporized tail gas, and the three-stage vaporized tail gas enters a tail gas treatment device to form a byproduct hydrochloric acid;
(6) Merging chlorine obtained by vaporization in the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer, and then feeding the merged chlorine into a synthesis reaction section from a chlorine inlet at the bottom of the synthesis reactor; crude acetic anhydride generated by the tail gas cooler, primary condensate generated by the primary vaporizer and crude acetic acid liquid generated by the tertiary vaporizer are converged into reaction feed liquid, and the reaction feed liquid enters the synthesis reactor from the feed liquid inlet to participate in reaction.
The invention has the following beneficial effects:
the synthesis reactor comprises a gas-liquid separation section and a synthesis reaction section, wherein the synthesis reaction section adopts a long tubular reaction cylinder, gas-liquid phase materials enter from the lower part of the synthesis reactor and flow out from the upper part of the synthesis reactor, the gas-liquid phase materials are fully contacted without back mixing, and the reaction conversion rate is improved. The synthesis reaction section of the synthesis reactor has a slender structure, and the self-generated reaction heat energy is transferred out more quickly through the circulating water of the jacket, so that the reaction condition is more stable, the occurrence of side reaction is inhibited, and the unit volume processing capacity of the synthesis reactor is improved.
The reaction tail gas is cooled by the tail gas cooler, and then condensed by the first-stage vaporizer, the second-stage vaporizer and the third-stage vaporizer in sequence, so that the property of deep refrigeration caused by heat absorption of liquid chlorine vaporization is fully utilized, the reaction tail gas is cooled and condensed, and is absorbed by raw materials, other substances except hydrogen chloride in the tail gas are collected and recycled to participate in the synthesis reaction of chloroacetic acid, the consumption of the raw materials is reduced, and meanwhile, the hydrogen chloride is purified, and finally, the qualified by-product industrial product hydrochloric acid is prepared.
Drawings
FIG. 1 is a schematic structural view of the present invention;
in the figure: 1. a circulating water inlet I; 2. a discharging liquid overflow port; 3. a pressure gauge port; 4. a thermometer port; 5. a gas phase outlet; 6. a safety valve port; 7. a level gauge port; 8. a gas-liquid separation section; 9. a first circulating water outlet; 10. a first jacket; 11. a circulating water outlet II; 12. a second jacket; 13. a synthesis reaction section; 14. a bubble breaker; 15. a liquid distributor; 16. a chlorine inlet; 17. a circulating water inlet II; 18. a feed liquid inlet; 19. a reaction tail gas inlet; 20. a tail gas cooler; 21. a circulating water outlet III; 22. a chloroacetic acid crude product tank; 23. a circulating water inlet III; 24. an anhydride inlet; 25. a cooling tail gas inlet; 26. a primary vaporizer; 27. a chlorine outlet III; 28. a third liquid chlorine inlet; 29. a first-stage vaporized tail gas inlet; 30. a chlorine outlet II; 31. a feed liquid inlet; 32. a second liquid chlorine inlet; 33. a secondary vaporizer; 34. a secondary vaporized tail gas inlet; 35. a tertiary vaporizer; 36. a chlorine gas outlet I; 37. a tail gas treatment device; 38. an acetic acid inlet; 39. and a first inlet for liquid chlorine.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
As shown in fig. 1, the chloroacetic acid synthesis system comprises a synthesis reactor, a tail gas cooler 20 and a vaporizer, wherein the synthesis reactor comprises a gas-liquid separation section 8 and a synthesis reaction section 13; the synthesis reaction section 13 adopts a long tubular reaction cylinder, the bottom of the synthesis reaction section 13 is provided with a chlorine inlet 16, and the side wall of the lower end of the synthesis reaction section 13 is provided with a feed liquid inlet 18; the top of the gas-liquid separation section 8 is provided with a gas phase outlet 5, and the upper end of the gas-liquid separation section 8 is provided with a liquid outlet overflow port 2; the vaporizer includes a first stage vaporizer 26, a second stage vaporizer 33, and a third stage vaporizer 35;
the gas phase outlet 5 is connected with a tail gas cooler 20, a first-stage vaporizer 26, a second-stage vaporizer 33 and a third-stage vaporizer 35 in sequence, the bottoms of the tail gas cooler 20, the first-stage vaporizer 26 and the third-stage vaporizer 35 are connected with a feeding liquid inlet 18, and the upper parts of the first-stage vaporizer 26, the second-stage vaporizer 33 and the third-stage vaporizer 35 are connected with a chlorine inlet 16; the discharge liquid overflow port 2 is connected with the upper part of a secondary vaporizer 33, and the bottom of the secondary vaporizer 33 is connected with a chloroacetic acid crude product tank 22.
Wherein:
the inlet 18 is connected with the liquid distributor 15 in the synthesis reaction section 13, and the bubble breaker 14 is also arranged in the synthesis reaction section 13.
The length-diameter ratio of the synthesis reaction section 13 is 5.
The top of the gas-liquid separation section 8 is also provided with a pressure gauge port 3, a temperature gauge port 4, a safety valve port 6 and a liquid level gauge port 7.
The outer wall of the gas-liquid separation section 8 is provided with a first jacket 10, the lower end of the first jacket 10 is provided with a first circulating water inlet 1, and the upper end of the first jacket 10 is provided with a first circulating water outlet 9; the outer wall of the synthesis reaction section 13 is provided with a second jacket 12, the lower end of the second jacket 12 is provided with a second circulating water inlet 17, and the upper end of the second jacket 12 is provided with a second circulating water outlet 11.
The upper part of the tail gas cooler 20 is provided with an acid anhydride inlet 24 and a circulating water outlet III 21, and the lower part of the tail gas cooler 20 is provided with a circulating water inlet III 23 and a reaction tail gas inlet 19; the reaction off-gas inlet 19 is connected to the gas phase outlet 5.
The upper part of the first-stage vaporizer 26 is provided with a chlorine outlet III 27, and the lower part of the first-stage vaporizer 26 is provided with a liquid chlorine inlet III 28 and a cooled tail gas inlet 25; the cooled tail gas inlet 25 is connected to the top of the tail gas cooler 20, and the chlorine outlet three 27 is connected to the chlorine inlet 16.
The upper part of the secondary vaporizer 33 is provided with a second chlorine outlet 30 and a feed liquid inlet 31, and the lower part of the secondary vaporizer 33 is provided with a second liquid chlorine inlet 32 and a first-stage vaporized tail gas inlet 29; the feed liquid inlet 31 is connected with the discharge liquid overflow port 2, the second chlorine outlet 30 is connected with the chlorine inlet 16, and the first-stage vaporized tail gas inlet 29 is connected with the top of the first-stage vaporizer 26.
The upper part of the third-stage vaporizer 35 is provided with an acetic acid inlet 38 and a chlorine outlet I36, and the lower part of the third-stage vaporizer 35 is provided with a liquid chlorine inlet I39 and a second-stage vaporized tail gas inlet 34; the first chlorine outlet 36 is connected with the chlorine inlet 16, and the second-stage vaporized tail gas inlet 34 is connected with the top of the second-stage vaporizer 33.
The top of the third-stage vaporizer 35 is connected with a tail gas treatment device 37.
The synthesis method of chloroacetic acid comprises the following steps:
(1) Reaction feed liquid enters the synthesis reaction section 13 from a feed liquid inlet 18 at the bottom of the synthesis reaction section 13 and uniformly flows out through a liquid distributor 15; chlorine gas is sprayed upwards from a chlorine gas inlet 16 at the bottom of the synthesis reaction section 13 to enter the synthesis reaction section 13 and is mixed with reaction feed liquid for chlorination reaction; chlorine gas and reaction feed liquid flow upward from the bottom of the synthesis reaction section 13 through the bubble breaker 14, so that the chlorine gas and the reaction feed liquid are uniformly contacted and reacted. After passing through the long reaction cylinder, the reaction is nearly completed, the material enters the gas-liquid separation section 8 at the upper part, the raw material is fully converted to generate reaction tail gas containing hydrogen chloride, the reaction tail gas enters the tail gas cooler 20 through the top gas phase outlet 5, and the reaction discharge liquid flows out through the feed liquid overflow port 2; the reaction heat generated in the synthesis reactor is carried out by the circulating water in the first jacket 10 and the second jacket 12. The pressure, temperature and liquid level in the synthesis reactor are respectively monitored by a pressure gauge, a temperature gauge and a liquid level gauge which are arranged in a pressure gauge port 3, a temperature gauge port 4 and a liquid level gauge port 7.
(2) Reaction tail gas contains substances such as hydrogen chloride, acetic acid, acyl chloride, chloroacetic acid and the like, enters the bottom of a tail gas cooler 20 from a reaction tail gas inlet 19, is cooled by circulating water, and the material part contained in the reaction tail gas is condensed to form condensate; then catalyst acetic anhydride is injected from an acid anhydride inlet 24 at the upper part of the tail gas cooler 20 to further absorb organic matters in the reaction tail gas, and the acetic anhydride and the condensate are mixed and flow out from the bottom of the tail gas cooler 20 to be called as crude acetic anhydride; the gas phase exits the top of the tail gas cooler 20, referred to as cooler tail gas, which enters the primary vaporizer 26.
(3) The tail gas of the cooler enters a primary vaporizer 26 from a cooling tail gas inlet 25, exchanges heat with liquid chlorine entering from a liquid chlorine inlet III 28, absorbs a large amount of heat in the vaporization process of the liquid chlorine to vaporize the heat into chlorine gas, so that part of organic phase in the tail gas of the cooler is deeply condensed to obtain primary condensate, and the rest tail gas is called primary vaporized tail gas; the primary vaporized tail gas exits the top of the primary vaporizer 26.
(4) The first-stage vaporized tail gas enters the second-stage vaporizer 33 from the first-stage vaporized tail gas inlet 29, the reaction discharge liquid flowing out of the liquid material overflow port 2 enters the second-stage vaporizer 33 from the liquid material inlet 31 and flows down, the first-stage vaporized tail gas blows off hydrogen chloride gas dissolved in the reaction discharge liquid, and the gas phase flows out of the top of the second-stage vaporizer 33 and is called second-stage vaporized tail gas; simultaneously, liquid chlorine is introduced from a second liquid chlorine inlet 32 at the lower part of the second-stage vaporizer 33, and the liquid chlorine absorbs the heat of the reaction discharge liquid to vaporize to form chlorine; the reaction discharge liquid flows out from the bottom of the secondary vaporizer 33 after being cooled and blown off, and enters a chloroacetic acid crude product tank 22 as a crude product for further deep treatment in subsequent working sections.
(5) The second-stage vaporized tail gas enters the third-stage vaporizer 35 through the second-stage vaporized tail gas inlet 34, exchanges heat with liquid chlorine entering the first liquid chlorine inlet 39, absorbs a large amount of heat in the vaporization process of the liquid chlorine, and is vaporized into chlorine gas, so that the second-stage vaporized tail gas is condensed deeply, the raw material acetic acid is injected into the third-stage vaporizer 35 from the acetic acid inlet 38 at the upper part of the third-stage vaporizer to be leached, organic matters in the second-stage vaporized tail gas are further absorbed, and then crude acetic acid liquid is formed; the treated tail gas flows out from the top of the three-stage vaporizer 35 and is called three-stage vaporized tail gas, and the three-stage vaporized tail gas enters the tail gas treatment device 37 to form a byproduct, namely hydrochloric acid.
(6) Chlorine obtained by vaporization in the first-stage vaporizer 26, the second-stage vaporizer 33 and the third-stage vaporizer 35 is merged and then enters the synthesis reaction section 13 from a chlorine inlet 16 at the bottom of the synthesis reactor; crude acetic anhydride generated by the tail gas cooler 20, primary condensate generated by the primary vaporizer 26 and crude acetic acid liquid generated by the tertiary vaporizer 35 are merged into reaction feed liquid, and the reaction feed liquid enters the synthesis reactor from the feed liquid inlet 18 to participate in reaction.
The chloroacetic acid is synthesized by adopting the system and the method, and the parameters in the reaction process are as follows:
the reaction temperature is 130 ℃, and the pressure is 4.8bar, the liquid chlorine is 173Kg/min, the acetic acid is 127Kg/min, and the acetic anhydride is 11.8Kg/min.
The single-pass conversion rate of the acetic acid is 96.5 percent, and the purity of the chloroacetic acid is 99.6 percent after the chloroacetic acid in the chloroacetic acid crude product tank 22 is rectified by a conventional rectification process.
Example 2
The chloroacetic acid synthesis system and method are the same as in example 1, and the parameters in the reaction process are as follows:
the length-diameter ratio of the synthesis reaction section 13 is 12, the reaction temperature is 145 ℃, and the pressure is 3.8bar, the feeding liquid chlorine is 180Kg/min, the acetic acid is 134Kg/min, and the acetic anhydride is 12.3Kg/min.
The conversion per pass of acetic acid is 97.2%, and the purity of chloroacetic acid is 99.5% after the chloroacetic acid in the crude chloroacetic acid product tank 22 is rectified by a conventional rectification process.
Example 3
The chloroacetic acid synthesis system and method are the same as in example 1, and the parameters in the reaction process are as follows:
the length-diameter ratio of the synthesis reaction section 13 is 20, the reaction temperature is 150 ℃, and under the condition of 4.5bar pressure, 192Kg/min of liquid chlorine, 142Kg/min of acetic acid and 12.9Kg/min of acetic anhydride are fed.
The single-pass conversion rate of the acetic acid is 95.7 percent, and the purity of the chloroacetic acid is 99.7 percent after the chloroacetic acid in the chloroacetic acid crude product tank 22 is rectified by a conventional rectification process.
Comparative example 1
The synthesis reactor is changed into the existing standard reaction kettle, the length-diameter ratio is 1, and the rest devices and the connection relation are the same as those in the example 1.
The effective volume of the existing standard reaction kettle is 10m 3 The method comprises the steps of feeding liquid chlorine of 75Kg/min, acetic acid of 55Kg/min, acetic anhydride of 5Kg/min, acetic acid conversion per pass of 80.5%, and the purity of chloroacetic acid is 98.1% after the crude product of chloroacetic acid is rectified by a conventional rectification process.
The synthesis reaction sections of the synthesis reactors of examples 1 to 3 of the invention have the same effective volume, which is 10m 3 And (6) counting.
Experiments prove that the raw material processing capacity of the synthesis reactor is 2.3-2.6 times of that of the existing standard reaction kettle, namely, the total amount of the raw materials processed in the synthesis reactor in a certain time is 2.3-2.6 times of that of the standard reaction kettle under the same reaction conditions.
The single-pass conversion rate of acetic acid is above 95.7%, and the purity of the chloroacetic acid crude product is above 99.5% after the chloroacetic acid crude product is rectified by a conventional rectification process. Therefore, the reaction conversion rate of the invention is greatly improved, and the purity of chloroacetic acid is correspondingly improved.
Claims (10)
1. A chloroacetic acid synthesis system comprises a synthesis reactor, a tail gas cooler (20) and a vaporizer, and is characterized in that: the synthesis reactor comprises a gas-liquid separation section (8) and a synthesis reaction section (13); the synthesis reaction section (13) adopts a long tubular reaction cylinder, the bottom of the synthesis reaction section (13) is provided with a chlorine inlet (16), and the side wall of the lower end of the synthesis reaction section (13) is provided with a feed liquid inlet (18); the top of the gas-liquid separation section (8) is provided with a gas phase outlet (5), and the upper end of the gas-liquid separation section (8) is provided with a discharge liquid overflow port (2); the vaporizer comprises a first-stage vaporizer (26), a second-stage vaporizer (33) and a third-stage vaporizer (35);
the gas phase outlet (5) is sequentially connected with the tail gas cooler (20), the first-stage vaporizer (26), the second-stage vaporizer (33) and the third-stage vaporizer (35), the bottoms of the tail gas cooler (20), the first-stage vaporizer (26) and the third-stage vaporizer (35) are respectively connected with the feed liquid inlet (18), and the upper parts of the first-stage vaporizer (26), the second-stage vaporizer (33) and the third-stage vaporizer (35) are respectively connected with the chlorine inlet (16); the discharge liquid overflow port (2) is connected with the upper part of a secondary vaporizer (33), and the bottom of the secondary vaporizer (33) is connected with a chloroacetic acid crude product tank (22);
the lower part of the first-stage vaporizer (26) is provided with a third liquid chlorine inlet (28); the lower part of the secondary vaporizer (33) is provided with a second liquid chlorine inlet (32); the lower part of the three-stage vaporizer (35) is provided with a first liquid chlorine inlet (39).
2. The chloroacetic acid synthesis system of claim 1, wherein: the feed liquid inlet (18) is connected with a liquid distributor (15) in the synthesis reaction section (13), and a bubble breaker (14) is also arranged in the synthesis reaction section (13); the length-diameter ratio of the synthesis reaction section (13) is 5-20.
3. The chloroacetic acid synthesis system of claim 1, wherein: the top of the gas-liquid separation section (8) is also provided with a pressure gauge port (3), a temperature gauge port (4), a safety valve port (6) and a liquid level gauge port (7).
4. The chloroacetic acid synthesis system of claim 1, wherein: a first jacket (10) is arranged on the outer wall of the gas-liquid separation section (8), a first circulating water inlet (1) is arranged at the lower end of the first jacket (10), and a first circulating water outlet (9) is arranged at the upper end of the first jacket (10); the outer wall of the synthesis reaction section (13) is provided with a second jacket (12), the lower end of the second jacket (12) is provided with a second circulating water inlet (17), and the upper end of the second jacket (12) is provided with a second circulating water outlet (11).
5. The chloroacetic acid synthesis system of claim 1, wherein: an anhydride inlet (24) and a circulating water outlet III (21) are arranged at the upper part of the tail gas cooler (20), and a circulating water inlet III (23) and a reaction tail gas inlet (19) are arranged at the lower part of the tail gas cooler (20); the reaction tail gas inlet (19) is connected with the gas phase outlet (5).
6. The chloroacetic acid synthesis system of claim 1, wherein: the upper part of the first-stage vaporizer (26) is provided with a chlorine outlet III (27), and the lower part of the first-stage vaporizer (26) is also provided with a cooling tail gas inlet (25); the cooled tail gas inlet (25) is connected with the top of the tail gas cooler (20), and the chlorine outlet III (27) is connected with the chlorine inlet (16).
7. The chloroacetic acid synthesis system of claim 1, wherein: the upper part of the secondary vaporizer (33) is provided with a chlorine outlet II (30) and a feed liquid inlet (31), and the lower part of the secondary vaporizer (33) is also provided with a primary vaporized tail gas inlet (29); the feed liquid inlet (31) is connected with the discharge liquid overflow port (2), the chlorine outlet II (30) is connected with the chlorine inlet (16), and the primary vaporized tail gas inlet (29) is connected with the top of the primary vaporizer (26).
8. The chloroacetic acid synthesis system of claim 1, wherein: the upper part of the third-stage vaporizer (35) is provided with an acetic acid inlet (38) and a chlorine gas outlet I (36), and the lower part of the third-stage vaporizer (35) is also provided with a second-stage vaporized tail gas inlet (34); the first chlorine outlet (36) is connected with the chlorine inlet (16), and the second-stage vaporized tail gas inlet (34) is connected with the top of the second-stage vaporizer (33).
9. The chloroacetic acid synthesis system of claim 1, wherein: the top of the three-stage vaporizer (35) is connected with a tail gas treatment device (37).
10. A chloroacetic acid synthesis process based on the system of any of claims 1 to 9, wherein: the method comprises the following steps:
(1) Reaction feed liquid enters the synthesis reaction section (13) from a feed liquid inlet (18) at the bottom of the synthesis reaction section (13) and uniformly flows out through a liquid distributor (15); chlorine gas is sprayed upwards from a chlorine gas inlet (16) at the bottom of the synthesis reaction section (13) and enters the synthesis reaction section (13); chlorine gas and reaction feed liquid flow upwards from the bottom of the synthesis reaction section (13), and the chlorine gas and the reaction feed liquid are uniformly contacted and reacted through a bubble breaker (14); after the reaction is finished, the material enters a gas-liquid separation section (8), the raw material is fully converted to generate reaction tail gas containing hydrogen chloride, the reaction tail gas enters a tail gas cooler (20) through a top gas phase outlet (5), and reaction discharge liquid flows out through a feed liquid overflow port (2);
(2) Reaction tail gas enters the bottom of a tail gas cooler (20) from a reaction tail gas inlet (19) and is cooled by circulating water, and materials contained in the reaction tail gas are condensed to form condensate; then catalyst acetic anhydride is injected from an acid anhydride inlet (24) at the upper part of the tail gas cooler (20) to further absorb organic matters in the reaction tail gas, and the acetic anhydride is mixed with condensate and flows out from the bottom of the tail gas cooler (20) to be called as crude acetic anhydride; the gas phase is discharged from the top of the tail gas cooler (20) and is called cooler tail gas, and the cooler tail gas enters a primary vaporizer (26);
(3) The tail gas of the cooler enters a primary vaporizer (26) from a cooling tail gas inlet (25) and exchanges heat with liquid chlorine entering from a liquid chlorine inlet III (28), the liquid chlorine absorbs heat and is vaporized into chlorine gas, so that an organic phase in the tail gas of the cooler is condensed to obtain primary condensate, and the rest tail gas is called primary vaporized tail gas; the primary vaporized tail gas is discharged from the top of the primary vaporizer (26);
(4) The primary vaporized tail gas enters a secondary vaporizer (33) from a primary vaporized tail gas inlet (29), the reaction discharge liquid flowing out of the feed liquid overflow port (2) enters the secondary vaporizer (33) from a feed liquid inlet (31) and flows down, the primary vaporized tail gas blows off hydrogen chloride gas dissolved in the reaction discharge liquid, and the gas phase flows out of the top of the secondary vaporizer (33) and is called secondary vaporized tail gas; simultaneously, liquid chlorine is introduced from a second liquid chlorine inlet (32) at the lower part of the second-stage vaporizer (33), and the liquid chlorine absorbs the heat of the reaction discharge liquid to be vaporized to form chlorine; the reaction discharge liquid flows out from the bottom of a secondary vaporizer (33) after being cooled and blown off, and enters a chloroacetic acid crude product tank (22) as a crude product for further deepening treatment in subsequent working sections;
(5) The second-stage vaporized tail gas enters the third-stage vaporizer (35) from the second-stage vaporized tail gas inlet (34) and exchanges heat with liquid chlorine entering from the first liquid chlorine inlet (39), the liquid chlorine absorbs heat and is vaporized into chlorine gas, so that the second-stage vaporized tail gas is condensed, the raw material acetic acid is injected and leached from the acetic acid inlet (38) at the upper part of the third-stage vaporizer (35), and after organic matters in the second-stage vaporized tail gas are further absorbed, crude acetic acid liquid is formed; the treated tail gas flows out from the top of the three-stage vaporizer (35) and is called as three-stage vaporized tail gas, and the three-stage vaporized tail gas enters a tail gas treatment device (37) to form a byproduct hydrochloric acid;
(6) Chlorine obtained by vaporization in the first-stage vaporizer (26), the second-stage vaporizer (33) and the third-stage vaporizer (35) is merged and then enters the synthesis reaction section (13) from a chlorine inlet (16) at the bottom of the synthesis reactor; crude acetic anhydride generated by the tail gas cooler (20), primary condensate generated by the primary vaporizer (26) and crude acetic acid liquid generated by the tertiary vaporizer (35) are merged into reaction feed liquid, and the reaction feed liquid enters the synthesis reactor from the feed liquid inlet (18) to participate in reaction.
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| US5401876A (en) * | 1992-07-23 | 1995-03-28 | Elf Atochem S.A. | Synthesis of chloroacetic acids |
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| CN109134231A (en) * | 2018-10-30 | 2019-01-04 | 杭州众立化工科技有限公司 | A kind of chloroacetic device and process of differential circulation continuous production |
| CN209974662U (en) * | 2019-01-29 | 2020-01-21 | 山东振兴化工有限公司 | Continuous production device for chloroacetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE1919476B2 (en) * | 1969-04-17 | 1977-06-16 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of monochloroacetic acid |
| CN104058947A (en) * | 2014-06-06 | 2014-09-24 | 中国天辰工程有限公司 | Chloroacetic acid production method capable of reducing acetic anhydride consumption |
| CN107586260A (en) * | 2016-07-08 | 2018-01-16 | 王玲 | A kind of chloroacetic preparation method |
| CN109851490A (en) * | 2019-03-01 | 2019-06-07 | 湖北泰盛化工有限公司 | The chloroacetic technique of acetic anhydride catalyst method continuous production |
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| US5401876A (en) * | 1992-07-23 | 1995-03-28 | Elf Atochem S.A. | Synthesis of chloroacetic acids |
| CN202199337U (en) * | 2011-05-30 | 2012-04-25 | 河南煤业化工集团研究院有限责任公司 | Continuous production device for chloroacetic acid |
| CN106242961A (en) * | 2016-07-29 | 2016-12-21 | 河北科技大学 | Production of chloroacetic acid equipment |
| CN109134231A (en) * | 2018-10-30 | 2019-01-04 | 杭州众立化工科技有限公司 | A kind of chloroacetic device and process of differential circulation continuous production |
| CN209974662U (en) * | 2019-01-29 | 2020-01-21 | 山东振兴化工有限公司 | Continuous production device for chloroacetic acid |
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