CN115745736B - Method for washing and purifying chlorinated alkane by utilizing microchannel reactor - Google Patents
Method for washing and purifying chlorinated alkane by utilizing microchannel reactor Download PDFInfo
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Abstract
The invention provides a method for washing and purifying chlorinated alkane by utilizing a microchannel reactor, belonging to the field of chlorinated alkane purification. The method for washing and purifying chlorinated alkane by utilizing the microchannel reactor comprises the following steps: primary water washing, secondary water washing, tertiary water washing, quaternary water washing and refining treatment. The method for washing and purifying the chlorinated alkane by utilizing the microchannel reactor provided by the invention realizes targeted removal of impurities in the chlorinated alkane crude product, effectively improves the washing efficiency, greatly reduces the water consumption in the washing process, reduces the production of washing waste liquid, effectively improves the washing effect, and reduces the pressure of subsequent refining treatment.
Description
Technical Field
The invention relates to the field of chlorinated alkane purification, in particular to a method for washing and purifying chlorinated alkane by utilizing a microchannel reactor.
Background
Chlorinated alkanes are an important class of organochlorine products, as well as important pharmaceutical intermediates, which find wide application in the field of fine organic chemistry. In the prior art, the preparation method of chloralkane mainly comprises the following steps: hydrochloric acid and organic alcohol are used as raw materials to prepare chloralkane; chlorine and hydrocarbon are used as raw materials to prepare chloralkane; other existing addition or substitution methods produce chlorinated alkanes.
At present, the industrial production method of chloralkane mainly comprises the following steps: hydrochloric acid and organic alcohol are used as raw materials to prepare chloralkane. Concretely, hydrochloric acid and organic alcohol are used as raw materials, under the condition of certain temperature and pressure (generally 70-110 ℃ and 0.3-0.4 MPa), the raw materials react under the catalysis of a catalyst to prepare a reaction solution, and the reaction solution is subjected to azeotropic distillation, standing and layering to prepare a chloralkane crude product; and (3) carrying out post-treatment processes such as water washing, rectification and the like on the chloralkane crude product to obtain chloralkane with higher purity.
However, the inventor researches that although the method can obtain better industrialized production effect, a certain amount of ether substances are generated during the reaction of hydrochloric acid and organic alcohol, a certain amount of organic alcohol and ether substances are distilled simultaneously during the azeotropic distillation of the reaction liquid, and thus, about 0.2-1wt% of organic alcohol, 0.2-1wt% of ether substances and a certain amount of water are present in the prepared crude chloroalkane product. Because of the existence of the impurities, the purification difficulty of the crude chloralkane product is high, the number of rectification and purification matching devices required in the follow-up process is large, the occupied area is large, the production energy consumption is high, and the production cost is high.
Further, in order to reduce the content of organic alcohol in the crude chloroalkane, water washing is generally used in the prior art. However, in order to reduce the organic alcohol content in the crude chloroalkane product to an ideal level, multistage washing is required, which has the problems of large water consumption, long washing time, large production amount of washing waste liquid and low washing efficiency in the washing process, and also has the problems of large number of washing equipment (usually a washing kettle with stirring), large occupied area and complicated washing process.
Furthermore, the inventor also discovers that a small amount of organic alcohol, ether substances and other impurities still exist in the prepared chlorinated alkane by the existing refining and purifying method for the crude chlorinated alkane, the purity of the chlorinated alkane is not more than 99.4%, the purity of the chlorinated alkane cannot be further improved, and the further expansion of the application field of the chlorinated alkane is limited.
Chinese patent CN114478182a discloses a device and method for producing chlorinated alkane series products, which uses organic alcohol and hydrochloric acid as raw materials to produce chlorinated alkane series products through four process procedures of a reaction section, a separation and refining section, an organic alcohol recovery section, and a crude product rectification section. However, the technical scheme has the defects that a certain amount of ether substances are produced in the reaction process of hydrochloric acid and organic alcohol, the difficulty of washing and purifying the crude chloralkane product is high, the number of rectification and purification matched devices required in the follow-up process is large, the occupied area is large, the production energy consumption is high, and the production cost is high; meanwhile, multistage water washing is needed, so that the efficiency is low; and the purity of the refined chlorinated alkane is 99.4% at the highest, and the purity index is required to be further improved.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a method for washing and purifying chlorinated alkane by utilizing a microchannel reactor, which aims at the advantages of simple and efficient purification process of a chlorinated alkane crude product, less required devices and effective reduction of the occupied area and the production energy consumption of related devices; the washing purification time is short, the production amount of washing waste liquid is small, and the washing efficiency is high; further improves the purity of the chloralkane.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for water washing and purifying chlorinated alkane by utilizing a microchannel reactor comprises the following steps: primary water washing, secondary water washing, tertiary water washing, quaternary water washing and refining treatment.
The primary water washing is carried out, and crude chloralkane and deionized water are introduced into a first reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the first reaction unit to be 50-60 ℃ and the water washing time to be 10-15min, and performing primary water washing to prepare primary water washing liquid;
a first reaction unit of the microchannel reactor is filled with a water-washing adsorbent; the filling amount of the water-washing adsorbent is 2-3wt% of the mass of the crude chlorohexane product;
in the primary water washing, the feeding rate of the crude chlorohexane is 90-110mL/min; the feeding rate of deionized water is 70-90mL/min.
The preparation method of the water-washing adsorbent comprises the following steps: and (5) pretreatment and molding.
The pretreatment, ball milling the zeolite and the fly ash with preset amounts uniformly to obtain mixed powder; washing the mixed powder sequentially by hydrochloric acid and sodium hydroxide solution, filtering, adding the mixed powder into pretreatment liquid with the volume of 3-6 times, heating to 50-60 ℃, stirring for 5-6 hours, filtering, and washing to neutrality by using enough deionized water to obtain a pretreatment substance.
Preferably, the pretreatment, putting zeolite and fly ash into a ball mill, controlling the ball-material ratio to be 6-9:1, ball milling for 20-40min, and performing ball milling treatment to obtain mixed powder; adding the mixed powder into hydrochloric acid with the volume of 2-5 times, heating to 35-45 ℃, stirring at 50-100rpm for 1-2 hours, and filtering; then putting into sodium hydroxide solution with the volume of 2-5 times, heating to 35-45 ℃, stirring at 50-100rpm for 2-3 hours, and filtering; continuously adding into 3-6 times of pretreatment liquid, heating to 50-60 ℃, stirring at 30-60rpm for 5-6 hours, filtering, and washing with enough deionized water to neutrality to obtain the pretreatment.
In the pretreatment, the weight ratio of the zeolite to the fly ash is 2.5-3.5:1;
the volume of crystal cavity of zeolite is 45-50% of total volume, and specific surface area is 700-800m 2 /g；
The concentration of the hydrochloric acid is 0.4-0.6mol/L;
the concentration of the sodium hydroxide solution is 0.4-0.6mol/L.
The pretreatment liquid is a mixture of di-sec-octyl maleate sodium sulfonate, laurinol polyoxyethylene ether, a silane coupling agent KH-550 and deionized water;
the weight ratio of the di-sec-octyl maleate sodium sulfonate, the laurinol polyoxyethylene ether, the silane coupling agent KH-550 and the deionized water is 0.01-0.02:0.02-0.03:0.05-0.08:150-180.
The shaping is carried out, after the pretreatment, the carboxymethyl cellulose and the polyvinyl alcohol 1799 are uniformly mixed, the mixture is granulated into particles with the particle size of 5-8mm, and the mixture is activated for 6-8 hours under the temperature condition of 110-120 ℃; and (3) at the temperature of 85-95 ℃, preserving heat and drying until the weight is unchanged, thus obtaining the water-washing adsorbent.
Preferably, the shaping is carried out, the pretreated matter, the carboxymethyl cellulose and the polyvinyl alcohol 1799 are put into a high-speed mixer, mixed for 15-30min at the mixing speed of 500-700rpm, granulated into particles with the particle size of 5-8mm, and then placed into a constant temperature box for heat preservation and activation for 6-8h at the temperature of 110-120 ℃; and (3) at the temperature of 85-95 ℃, preserving heat and drying until the weight is unchanged, and obtaining the water-washing adsorption.
The weight ratio of the pretreatment to the carboxymethyl cellulose to the polyvinyl alcohol 1799 is 100:1-2:0.3-0.5.
The secondary washing liquid is used for introducing the primary washing liquid and deionized water into a second reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the second reaction unit to be 45-55 ℃ and the water washing time to be 20-30min, and performing secondary water washing to obtain secondary water washing liquid.
A second reaction unit of the microchannel reactor is filled with a water-washing adsorbent; the water-washed adsorbent is the same as the water-washed adsorbent in the primary water washing; the filling amount of the water washing adsorbent is 1-2wt% of the mass of the secondary water washing liquid.
In the secondary water washing, the feeding rate of deionized water is 55-65% of the feeding rate of primary water washing liquid.
The third-stage water washing is carried out, and the second-stage water washing liquid and deionized water are led into a third reaction unit of the microchannel reactor at a preset feeding rate; and controlling the temperature of the third reaction unit to be 40-50 ℃ and the water washing time to be 10-15min, and performing three-stage water washing to obtain three-stage water washing liquid.
A third reaction unit of the microchannel reactor is filled with a water-washing adsorbent; the water-washed adsorbent is the same as the water-washed adsorbent in the primary water washing; the filling amount of the water washing adsorbent is 1-2wt% of the mass of the three-stage water washing liquid.
In the three-stage water washing, the feeding rate of deionized water is 55-65% of the feeding rate of the second-stage water washing liquid.
The four-stage washing liquid is used for guiding the three-stage washing liquid and deionized water into a fourth reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the fourth reaction unit to be 30-40 ℃ and the water washing time to be 10-15min, and carrying out four-stage water washing to obtain four-stage water washing liquid.
In the four-stage water washing, the feeding rate of deionized water is 30-40% of the feeding rate of the three-stage water washing liquid.
The quaternary water washing liquid is refined to prepare chloralkane.
And (3) refining, filtering and layering the quaternary water washing liquid, and rectifying the layered upper liquid to obtain chloralkane.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for washing and purifying chlorinated alkane by utilizing the microchannel reactor, disclosed by the invention, the chlorinated alkane is washed and purified by utilizing the microchannel reactor, one to four stages of washing steps are arranged, and meanwhile, a specific washing adsorbent is matched in the one to three stages of washing processes, so that the targeted removal of impurities in the chlorinated alkane crude product is realized, the washing efficiency is effectively improved, the water consumption in the washing process is greatly reduced, the production amount of washing waste liquid is reduced, the washing effect is effectively improved, and the pressure of subsequent refining treatment is reduced.
(2) The method for washing and purifying the chlorinated alkane by utilizing the microchannel reactor effectively realizes the targeted removal of impurities in the chlorinated alkane crude product, the purity of the prepared chlorinated alkane product can reach 99.86-99.91%, the further improvement of the chlorinated alkane purity can be realized under the conditions of high washing efficiency, low washing water consumption and low rectifying energy consumption, and the method provides possibility for the further expansion of the chlorinated alkane application field.
(3) According to the method for washing and purifying chlorinated alkane by utilizing the microchannel reactor, the total dosage of deionized water is only 2.2-2.5 times of the volume of the crude product of chlorohexane in the one-to-four-stage washing process through statistics; compared with the prior art, the water consumption in the water washing process is reduced by about 44.4-51.1%, the water resource is effectively saved, the production cost is greatly reduced, the production amount of water washing waste liquid is effectively reduced, and the wastewater treatment cost is reduced.
(4) The method for washing and purifying the chlorinated alkane by utilizing the microchannel reactor has the advantages of simple washing and purifying process, high washing and purifying efficiency and good effect, effectively reduces the pressure of subsequent rectifying and purifying, reduces the occupied area of related devices and the production energy consumption, and reduces the production cost of enterprises.
Drawings
FIG. 1 is a liquid chromatogram of the chlorohexane product obtained in example 1.
FIG. 2 is a liquid chromatogram of the chlorohexane product obtained in example 2.
FIG. 3 is a liquid chromatogram of the chlorohexane product obtained in example 3.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A process for washing and purifying chloroalkane by micro-channel reactor includes such steps as preparing reaction liquid from chlorohexane by synthetic reaction of hydrochloric acid and n-hexanol, rectifying by azeotropic distillation tower, condensing, collecting overhead, laying aside for layering, and overflow of the crude chlorohexane to intermediate tank.
Through detection, in the crude product of the chlorohexane, the content of the chlorohexane is 94.13 weight percent, the content of the n-hexanol is 0.62 weight percent, the content of ether substances (mainly hexyl ether) is 0.31 weight percent, the content of hydrogen chloride is 0.08 weight percent, and the balance is water.
In this example 1, the micro-channel reactor was used to wash and purify chlorohexane, and the specific procedure is as follows:
1. first-stage water washing
The crude chlorohexane product temporarily stored in the intermediate tank is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; simultaneously, deionized water is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; and (5) performing primary water washing. Wherein, the first reaction unit of the microchannel reactor is filled with water washing adsorbent; the temperature of the first reaction unit is controlled to be 50 ℃, and the water washing time of the materials in the first reaction unit is controlled to be 10min, so that the primary water washing liquid is prepared.
In the primary water washing process, the feeding rate of the crude chlorohexane is 90mL/min; the deionized water feed rate was 70mL/min.
The loading of the water-washed adsorbent was 2wt% of the mass of the crude chlorohexane product.
The water-washed adsorbent is prepared by the following steps:
1) Pretreatment of
Putting zeolite and fly ash into a ball mill, controlling the ball-material ratio to be 6:1, and performing ball milling for 20min to obtain mixed powder; adding the mixed powder into hydrochloric acid with the volume of 2 times, heating to 35 ℃, stirring at 50rpm for 1h, and filtering; then put into sodium hydroxide solution with the volume of 2 times, heated to 35 ℃, stirred for 2 hours at 50rpm and filtered; continuously adding the mixture into 3 times of pretreatment liquid, heating to 50 ℃, stirring at 30rpm for 5 hours, filtering out, and flushing with enough deionized water to be neutral to obtain a pretreatment substance.
Wherein the weight ratio of the zeolite to the fly ash is 2.5:1.
The volume of the crystal cavities of the zeolite is 45 percent of the total volume, and the specific surface area is 700m 2 /g。
The concentration of hydrochloric acid is 0.4mol/L.
The concentration of the sodium hydroxide solution was 0.4mol/L.
The pretreatment liquid is prepared by adding di-sec-octyl maleate sodium sulfonate, laurinol polyoxyethylene ether and silane coupling agent KH-550 into deionized water, and dispersing uniformly.
Wherein, the weight ratio of the di-sec-octyl maleate sodium sulfonate, the laurinol polyoxyethylene ether, the silane coupling agent KH-550 and the deionized water is 0.01:0.02:0.05:150.
2) Shaping
Putting the pretreatment, carboxymethyl cellulose and polyvinyl alcohol 1799 into a high-speed mixer, mixing at 500rpm for 15min, granulating into particles with the particle size of 5mm, and then placing into a constant temperature box for heat preservation and activation for 6h at the temperature of 110 ℃; and (3) at the temperature of 85 ℃, preserving heat and drying until the weight is unchanged, thus obtaining the water-washing adsorbent.
Wherein the weight ratio of the pretreatment to the carboxymethyl cellulose to the polyvinyl alcohol 1799 is 100:1:0.3.
2. Two-stage water washing
The primary water washing liquid passes through a second reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 45 ℃, and controlling the water washing time of the primary water washing liquid in the second reaction unit to be 20 minutes to prepare the secondary water washing liquid.
In the secondary water washing process, the feeding rate of deionized water is 55% of the feeding rate of the primary water washing liquid.
The loading of the water washing adsorbent is 1wt% of the mass of the primary water washing liquid; and the water-washed adsorbent used in the second water-washed step is the same as the water-washed adsorbent used in the first water-washed step.
3. Three-stage water washing
The second-stage water washing liquid passes through a third reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the third reaction unit to be 40 ℃, and controlling the water washing time of the second-stage water washing liquid in the third reaction unit to be 20min to prepare the third-stage water washing liquid.
In the three-stage water washing process, the feeding rate of deionized water is 55% of the feeding rate of the secondary water washing liquid.
The filling amount of the water washing adsorbent is 1wt% of the mass of the secondary water washing liquid; and the water-washed adsorbent adopted in the three-stage water-washing step is the same as the water-washed adsorbent adopted in the first-stage water-washing step.
4. Four-stage water washing
The tertiary water washing liquid passes through a fourth reaction unit of the microchannel reactor; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 30 ℃, and controlling the water washing time of the third-stage water washing liquid in the fourth reaction unit to be 10min to prepare the fourth-stage water washing liquid.
In the four-stage water washing process, the feeding rate of deionized water is 30% of the feeding rate of the three-stage water washing liquid.
5. Refining treatment
And filtering the four-stage water washing liquid to remove solid matters, standing for layering, overflowing the upper liquid to a buffer tank for temporary storage, and then entering a rectifying tower for rectification to obtain the chlorohexane product of the embodiment 1.
Wherein, the rectification for chlorohexane can be carried out by adopting the existing chlorohexane rectification technology.
The detection shows that in the chlorohexane product of example 1, the content of chlorohexane is 99.86%, the content of organic alcohol is 0.07%, and the content of ether substances is 0.01%.
Further, by statistics, in the method for water washing and purifying chlorinated alkane by using the micro-channel reactor in the embodiment 1, the total amount of deionized water is about 2.2 times of the volume of the crude product of chlorohexane in the one-to-four-stage water washing process.
Further, compared with the process of washing chlorinated alkane by adopting a washing kettle in the prior art, according to the three-stage washing process, the water consumption of each stage of washing is calculated according to 1.5 times of the volume of the crude product of the chlorohexane, and the total water consumption of the washing kettle in the prior art is 4.5 times of the volume of the crude product of the chlorohexane. The water consumption of example 1 was reduced by about 51.1% compared to the prior art.
Example 2
A process for washing and purifying chloroalkane by micro-channel reactor includes such steps as preparing reaction liquid from chlorohexane by synthetic reaction of hydrochloric acid and n-hexanol, rectifying by azeotropic distillation tower, condensing, collecting overhead, laying aside for layering, and overflow of the crude chlorohexane to intermediate tank.
Through detection, in the crude product of the chlorohexane, the content of the chlorohexane is 94.13 weight percent, the content of the n-hexanol is 0.62 weight percent, the content of ether substances (mainly hexyl ether) is 0.31 weight percent, the content of hydrogen chloride is 0.08 weight percent, and the balance is water.
In this example 2, the micro-channel reactor was used to wash and purify chlorohexane, and the specific procedure is as follows:
1. first-stage water washing
The crude chlorohexane product temporarily stored in the intermediate tank is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; simultaneously, deionized water is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; and (5) performing primary water washing. Wherein, the first reaction unit of the microchannel reactor is filled with water washing adsorbent; the temperature of the first reaction unit is controlled to be 55 ℃, and the water washing time of the materials in the first reaction unit is 13min, so that the primary water washing liquid is prepared.
In the primary water washing process, the feeding rate of the crude chlorohexane is 100mL/min; the deionized water feed rate was 80mL/min.
The loading of the water-washed adsorbent was 2.5wt% based on the mass of the crude chlorohexane product.
The water-washed adsorbent is prepared by the following steps:
1) Pretreatment of
Putting zeolite and fly ash into a ball mill, controlling the ball-material ratio to be 8:1, and performing ball milling for 30min to obtain mixed powder; adding the mixed powder into hydrochloric acid with the volume being 3 times that of the mixed powder, heating to 40 ℃, stirring at 80rpm for 1.5 hours, and filtering out; then put into sodium hydroxide solution with 3 times of volume, heated to 40 ℃, stirred for 2.5 hours at 80rpm and filtered; continuously adding the mixture into 5 times of pretreatment liquid, heating to 55 ℃, stirring at 50rpm for 5.5 hours, filtering out, and flushing with enough deionized water to be neutral to obtain a pretreatment substance.
Wherein the weight ratio of the zeolite to the fly ash is 3:1.
The volume of the crystal cavity of the zeolite is 47% of the total volume, and the specific surface area is 760m 2 /g。
The concentration of hydrochloric acid is 0.5mol/L.
The concentration of the sodium hydroxide solution was 0.5mol/L.
The pretreatment liquid is prepared by adding di-sec-octyl maleate sodium sulfonate, laurinol polyoxyethylene ether and silane coupling agent KH-550 into deionized water, and dispersing uniformly.
Wherein, the weight ratio of the di-sec-octyl maleate sodium sulfonate, the laurinol polyoxyethylene ether, the silane coupling agent KH-550 and the deionized water is 0.015:0.025:0.07:160.
2) Shaping
Putting the pretreatment, carboxymethyl cellulose and polyvinyl alcohol 1799 into a high-speed mixer, mixing at 600rpm for 25min, granulating into particles with the particle size of 7mm, and then placing into a constant temperature box for heat preservation and activation for 7h at 115 ℃; and (3) at the temperature of 90 ℃, preserving heat and drying until the weight is unchanged, thus obtaining the water-washing adsorbent.
Wherein the weight ratio of the pretreatment to the carboxymethyl cellulose to the polyvinyl alcohol 1799 is 100:1.5:0.4.
2. Two-stage water washing
The primary water washing liquid passes through a second reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 50 ℃, and controlling the water washing time of the primary water washing liquid in the second reaction unit to be 25 minutes to prepare the secondary water washing liquid.
In the secondary water washing process, the feeding rate of deionized water is 60% of the feeding rate of the primary water washing liquid.
The loading of the water washing adsorbent is 1.5wt% of the mass of the primary water washing liquid; and the water-washed adsorbent used in the second water-washed step is the same as the water-washed adsorbent used in the first water-washed step.
3. Three-stage water washing
The second-stage water washing liquid passes through a third reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the third reaction unit to be 45 ℃, and controlling the water washing time of the second-stage water washing liquid in the third reaction unit to be 25 minutes to prepare the third-stage water washing liquid.
In the three-stage water washing process, the feeding rate of deionized water is 60% of the feeding rate of the secondary water washing liquid.
The filling amount of the water washing adsorbent is 1.5 weight percent of the mass of the secondary water washing liquid; and the water-washed adsorbent adopted in the three-stage water-washing step is the same as the water-washed adsorbent adopted in the first-stage water-washing step.
4. Four-stage water washing
The tertiary water washing liquid passes through a fourth reaction unit of the microchannel reactor; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 35 ℃, and controlling the water washing time of the third-stage water washing liquid in the fourth reaction unit to be 12min to prepare the fourth-stage water washing liquid.
In the four-stage water washing process, the feeding rate of deionized water is 35% of the feeding rate of the three-stage water washing liquid.
5. Refining treatment
And filtering the four-stage water washing liquid to remove solid matters, standing for layering, overflowing the upper liquid to a buffer tank for temporary storage, and then entering a rectifying tower for rectification to obtain the chlorohexane product of the embodiment 2.
Wherein, the rectification for chlorohexane can be carried out by adopting the existing chlorohexane rectification technology.
The detection shows that in the chlorohexane product of example 2, the content of chlorohexane is 99.91%, the content of organic alcohol is 0.07%, and the content of ether substances is 0.01%.
Further, by statistics, in the method for water washing and purifying chlorinated alkane by using the micro-channel reactor in the embodiment 2, the total amount of deionized water is about 2.35 times of the volume of the crude product of chlorohexane in the one-to-four-stage water washing process.
Further, compared with the process of washing chlorinated alkane by adopting a washing kettle in the prior art, according to the three-stage washing process, the water consumption of each stage of washing is calculated according to 1.5 times of the volume of the crude product of the chlorohexane, and the total water consumption of the washing kettle in the prior art is 4.5 times of the volume of the crude product of the chlorohexane. The water consumption of example 2 was reduced by about 47.8% compared to the prior art.
Example 3
A process for washing and purifying chloroalkane by micro-channel reactor includes such steps as preparing reaction liquid from chlorohexane by synthetic reaction of hydrochloric acid and n-hexanol, rectifying by azeotropic distillation tower, condensing, collecting overhead, laying aside for layering, and overflow of the crude chlorohexane to intermediate tank.
Through detection, in the crude product of the chlorohexane, the content of the chlorohexane is 94.13 weight percent, the content of the n-hexanol is 0.62 weight percent, the content of ether substances (mainly hexyl ether) is 0.31 weight percent, the content of hydrogen chloride is 0.08 weight percent, and the balance is water.
In this example 3, the micro-channel reactor was used to wash and purify chlorohexane, and the specific procedure is as follows:
1. first-stage water washing
The crude chlorohexane product temporarily stored in the intermediate tank is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; simultaneously, deionized water is introduced into a first reaction unit of the microchannel reactor at a predetermined feed rate; and (5) performing primary water washing. Wherein, the first reaction unit of the microchannel reactor is filled with water washing adsorbent; the temperature of the first reaction unit is controlled to be 60 ℃, and the water washing time of the materials in the first reaction unit is 15min, so that the primary water washing liquid is prepared.
In the primary water washing process, the feeding rate of the crude chlorohexane product is 110mL/min; the deionized water feed rate was 90mL/min.
The loading of the water-washed adsorbent was 3wt% of the mass of the crude chlorohexane product.
The water-washed adsorbent is prepared by the following steps:
1) Pretreatment of
Putting zeolite and fly ash into a ball mill, controlling the ball-material ratio to be 9:1, and performing ball milling for 40min to obtain mixed powder; adding the mixed powder into hydrochloric acid with the volume of 5 times, heating to 45 ℃, stirring at 100rpm for 2 hours, and filtering; then put into sodium hydroxide solution with 5 times of volume, heated to 45 ℃, stirred for 3 hours at 100rpm and filtered; continuously adding the mixture into pretreatment liquid with the volume of 6 times, heating to 60 ℃, stirring at 60rpm for 6 hours, filtering out, and flushing with enough deionized water to be neutral to obtain a pretreatment substance.
Wherein the weight ratio of the zeolite to the fly ash is 3.5:1.
The volume of the crystal cavities of the zeolite is 50% of the total volume, and the specific surface area is 800m 2 /g。
The concentration of hydrochloric acid is 0.6mol/L.
The concentration of the sodium hydroxide solution was 0.6mol/L.
The pretreatment liquid is prepared by adding di-sec-octyl maleate sodium sulfonate, laurinol polyoxyethylene ether and silane coupling agent KH-550 into deionized water, and dispersing uniformly.
Wherein, the weight ratio of the di-sec-octyl maleate sodium sulfonate, the laurinol polyoxyethylene ether, the silane coupling agent KH-550 and the deionized water is 0.02:0.03:0.08:180.
2) Shaping
Putting the pretreatment, carboxymethyl cellulose and polyvinyl alcohol 1799 into a high-speed mixer, mixing at a mixing speed of 700rpm for 30min, granulating into particles with a particle size of 8mm, and then placing into a constant temperature box for heat preservation and activation for 8h at a temperature of 120 ℃; and (3) at the temperature of 95 ℃, preserving heat and drying until the weight is unchanged, thus obtaining the water-washing adsorbent.
Wherein the weight ratio of the pretreatment to the carboxymethyl cellulose to the polyvinyl alcohol 1799 is 100:2:0.5.
2. Two-stage water washing
The primary water washing liquid passes through a second reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 55 ℃, and controlling the water washing time of the primary water washing liquid in the second reaction unit to be 30 minutes to prepare the secondary water washing liquid.
In the secondary water washing process, the feeding rate of deionized water is 65% of the feeding rate of the primary water washing liquid.
The loading of the water washing adsorbent is 2wt% of the mass of the primary water washing liquid; and the water-washed adsorbent used in the second water-washed step is the same as the water-washed adsorbent used in the first water-washed step.
3. Three-stage water washing
The second-stage water washing liquid passes through a third reaction unit of the microchannel reactor filled with water washing adsorbent; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the third reaction unit to be 50 ℃, and controlling the water washing time of the second-stage water washing liquid in the third reaction unit to be 30min to prepare the third-stage water washing liquid.
In the three-stage water washing process, the feeding rate of deionized water is 65% of the feeding rate of the secondary water washing liquid.
The filling amount of the water washing adsorbent is 2wt% of the mass of the secondary water washing liquid; and the water-washed adsorbent adopted in the three-stage water-washing step is the same as the water-washed adsorbent adopted in the first-stage water-washing step.
4. Four-stage water washing
The tertiary water washing liquid passes through a fourth reaction unit of the microchannel reactor; simultaneously, deionized water is introduced into a second reaction unit of the microchannel reactor at a predetermined feed rate; and controlling the temperature of the second reaction unit to be 40 ℃, and controlling the water washing time of the third-stage water washing liquid in the fourth reaction unit to be 15min to prepare the fourth-stage water washing liquid.
In the four-stage water washing process, the feeding rate of deionized water is 40% of the feeding rate of the three-stage water washing liquid.
5. Refining treatment
And filtering the four-stage water washing liquid to remove solid matters, standing for layering, overflowing the upper liquid to a buffer tank for temporary storage, and then entering a rectifying tower for rectification to obtain the chlorohexane product of the embodiment 3.
Wherein, the rectification for chlorohexane can be carried out by adopting the existing chlorohexane rectification technology.
The detection shows that in the chlorohexane product of example 3, the content of chlorohexane is 99.90%, the content of organic alcohol is 0.05%, and the content of ether is 0.01%.
Further, by statistics, in the method for water-washing and purifying chlorinated alkane by using the micro-channel reactor in the embodiment 3, the total amount of deionized water is about 2.5 times of the volume of the crude product of chlorohexane in the one-to-four-stage water washing process.
Further, compared with the process of washing chlorinated alkane by adopting a washing kettle in the prior art, according to the three-stage washing process, the water consumption of each stage of washing is calculated according to 1.5 times of the volume of the crude product of the chlorohexane, and the total water consumption of the washing kettle in the prior art is 4.5 times of the volume of the crude product of the chlorohexane. The water consumption of example 3 was reduced by about 44.4% compared to the prior art.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) Omitting the steps of three-stage washing and four-stage washing; 2) In the primary water washing and the secondary water washing, zeolite is adopted to replace a water washing adsorbent.
According to detection, in the chlorohexane product prepared in the comparative example 1, the content of chlorohexane is 99.69%, the content of organic alcohol is 0.18%, and the content of ether substances is 0.10%.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In the preparation of the water-washing adsorbent, in the pretreatment process, pretreatment liquid treatment is omitted, and after the mixed powder is washed by sodium hydroxide solution, the mixed powder is washed to be neutral by enough deionized water to prepare a pretreatment object; 2) In the preparation of the water-washing adsorbent, carboxymethyl cellulose and polyvinyl alcohol 1799 are omitted in the molding process.
Through detection, in the chlorohexane product prepared in the comparative example 2, the content of chlorohexane is 99.83%, the content of organic alcohol is 0.09%, and the content of ether substances is 0.06%.
According to the invention, the micro-channel reactor is utilized to carry out water washing purification on chlorinated alkane, one to four stages of water washing steps are arranged, and meanwhile, a specific water washing adsorbent is matched in the one to three stages of water washing processes, so that the targeted removal of impurities in the chlorinated alkane crude product is realized, the water washing efficiency is effectively improved, the water consumption in the water washing process is greatly reduced, the water washing waste liquid production is reduced, the water washing effect is effectively improved, and the pressure of the subsequent refining treatment is lightened. As can be seen from comparative example 1, the steps of three-stage washing and four-stage washing are omitted, and after zeolite is adopted to replace a washing adsorbent, the targeted removal of impurities in the crude chlorinated alkane product cannot be realized, the washing effect is not ideal, the purity of the prepared chlorinated alkane product is reduced, and the impurity content is increased. As can be seen from comparative example 2, in the preparation of the water-washed adsorbent, the pretreatment liquid during pretreatment is omitted, and the specific adsorption capacity of the water-washed adsorbent to alcohol and ether impurities contained in the crude chloroalkane product is reduced after the carboxymethyl cellulose and polyvinyl alcohol 1799 during molding are omitted.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for water washing and purifying chlorinated alkane by utilizing a microchannel reactor, which is characterized by comprising the following steps: primary water washing, secondary water washing, tertiary water washing, quaternary water washing and refining treatment;
the primary water washing is carried out, and crude chloralkane and deionized water are introduced into a first reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the first reaction unit to be 50-60 ℃ and the water washing time to be 10-15min, and performing primary water washing to prepare primary water washing liquid;
a first reaction unit of the microchannel reactor is filled with a water-washing adsorbent;
the preparation method of the water-washing adsorbent comprises the following steps: pretreatment and molding;
the pretreatment, ball milling the zeolite and the fly ash with preset amounts uniformly to obtain mixed powder; washing the mixed powder sequentially by hydrochloric acid and sodium hydroxide solution, filtering, adding the mixed powder into pretreatment liquid with the volume of 3-6 times, heating to 50-60 ℃, stirring for 5-6 hours, filtering, and washing to neutrality by using enough deionized water to obtain a pretreatment substance;
the pretreatment liquid is a mixture of di-sec-octyl maleate sodium sulfonate, laurinol polyoxyethylene ether, a silane coupling agent KH-550 and deionized water;
the shaping is carried out, after the pretreatment, the carboxymethyl cellulose and the polyvinyl alcohol 1799 are uniformly mixed, the mixture is granulated into particles with the particle size of 5-8mm, and the mixture is activated for 6-8 hours under the temperature condition of 110-120 ℃; keeping the temperature and drying the mixture at the temperature of 85-95 ℃ until the weight is unchanged, and preparing the water-washing adsorbent;
the secondary washing liquid is used for introducing the primary washing liquid and deionized water into a second reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the second reaction unit to be 45-55 ℃ and the water washing time to be 20-30min, and performing secondary water washing to obtain secondary water washing liquid;
a second reaction unit of the microchannel reactor is filled with a water-washing adsorbent; the water-washed adsorbent is the same as the water-washed adsorbent in the primary water washing;
the third-stage water washing is carried out, and the second-stage water washing liquid and deionized water are led into a third reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the third reaction unit to be 40-50 ℃ and the water washing time to be 10-15min, and performing three-stage water washing to prepare three-stage water washing liquid;
a third reaction unit of the microchannel reactor is filled with a water-washing adsorbent; the water-washed adsorbent is the same as the water-washed adsorbent in the primary water washing;
the four-stage washing liquid is used for guiding the three-stage washing liquid and deionized water into a fourth reaction unit of the microchannel reactor at a preset feeding rate; controlling the temperature of the fourth reaction unit to be 30-40 ℃ and the water washing time to be 10-15min, and performing four-stage water washing to obtain four-stage water washing liquid;
the quaternary water washing liquid is refined to prepare chloralkane.
2. The method for water-washing and purifying chlorinated alkane by utilizing a micro-channel reactor according to claim 1, wherein in the primary water washing, the feeding rate of the crude chlorohexane is 90-110mL/min; the feeding rate of deionized water is 70-90mL/min;
in the secondary water washing, the feeding rate of deionized water is 55-65% of the feeding rate of primary water washing liquid;
in the three-stage water washing, the feeding rate of deionized water is 55-65% of the feeding rate of the second-stage water washing liquid;
in the four-stage water washing, the feeding rate of deionized water is 30-40% of the feeding rate of the three-stage water washing liquid.
3. The method for water washing purification of chlorinated alkane by utilizing a micro-channel reactor according to claim 1, wherein in the primary water washing, the loading amount of the water washing adsorbent is 2-3wt% of the crude product of chlorohexane;
in the secondary water washing, the filling amount of the water washing adsorbent is 1-2wt% of the mass of the secondary water washing liquid;
in the three-stage water washing, the loading of the water washing adsorbent is 1-2wt% of the mass of the three-stage water washing liquid.
4. The method for water-washing and purifying chlorinated alkane by utilizing a microchannel reactor according to claim 1, wherein in the pretreatment, the weight ratio of zeolite to fly ash is 2.5-3.5:1;
the volume of crystal cavity of zeolite is 45-50% of total volume, and specific surface area is 700-800m 2 /g。
5. The method for water-washing purification of chlorinated alkane by micro-channel reactor according to claim 1, wherein the concentration of hydrochloric acid in the pretreatment is 0.4-0.6mol/L; the concentration of the sodium hydroxide solution is 0.4-0.6mol/L.
6. The method for water washing and purifying chlorinated alkane by utilizing a microchannel reactor according to claim 1, wherein the pretreatment liquid comprises sodium di-sec-octyl maleate sulfonate, lauryl polyoxyethylene ether, silane coupling agent KH-550 and deionized water in a weight ratio of 0.01-0.02:0.02-0.03:0.05-0.08:150-180.
7. The method for water washing and purifying chlorinated alkane by utilizing a microchannel reactor according to claim 1, wherein the ratio of the pretreatment, carboxymethyl cellulose and polyvinyl alcohol 1799 in parts by weight in the molding is 100:1-2:0.3-0.5.
8. The method for water washing and purifying chlorinated alkane by utilizing a microchannel reactor as claimed in claim 1, wherein the chlorinated alkane is prepared by rectifying the upper liquid obtained by filtering and layering the four-stage water washing liquid.
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