CN112619395A - Tail gas absorption process for producing chloromethyl ethyl ether by high-purity hydrogen chloride method - Google Patents
Tail gas absorption process for producing chloromethyl ethyl ether by high-purity hydrogen chloride method Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims abstract description 122
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 117
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 117
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 115
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 93
- 230000008569 process Effects 0.000 title claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 187
- 239000007788 liquid Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 19
- 229920002866 paraformaldehyde Polymers 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000005070 sampling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000002699 waste material Substances 0.000 description 11
- 239000012267 brine Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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Abstract
The invention provides a tail gas absorption process for producing chloromethyl ethyl ether by a high-purity hydrogen chloride method, which adopts a device which is completely the same as a main reaction device for producing the chloromethyl ethyl ether as a tail gas absorption device; and the tail gas of the main reaction device is conducted through a pipeline and is introduced into the feed liquid in the tail gas absorption device to carry out tail gas absorption reaction. The invention has the beneficial effects that: the excessive hydrogen chloride tail gas can be completely absorbed through reaction to generate chloromethyl ethyl ether, so that the aims of eradicating the tail gas, saving raw materials, recycling, reducing cost and protecting the environment are fulfilled; after tail gas absorption, the conversion rate of the prepared chloromethyl ethyl ether is more than 82 percent, and the purity is more than 95 percent; when the prepared chloromethyl ethyl ether is used in the synthesis process of the chlorfenapyr, the conversion rate of the chlorfenapyr can be improved by 2-5%.
Description
Technical Field
The invention relates to the field of tail gas treatment, in particular to a tail gas absorption process for producing chloromethyl ethyl ether by a high-purity hydrogen chloride method.
Background
Chloromethyl ethyl ether is an important chemical product, has wide application, is mainly applied to organic synthesis reaction, is a main raw material of pesticide herbicide acetochlor and pesticide chlorfenapyr, and can also be used for synthesis production of other resin products.
The synthesis method of chloromethyl ethyl ether is more, and because the synthesis method of high-purity hydrogen chloride, paraformaldehyde and absolute ethyl alcohol is adopted, the conversion rate is high, the process wastewater generated in the reaction process is less, no waste residue is generated, the product purity is high, and the synthesis method is an advanced synthesis mode in the current synthesis method of chloromethyl ethyl ether, so the method also becomes the hotspot of research of people.
The applicant found that in the production of chloromethyl ethyl ether by the above-mentioned method, excess hydrogen chloride extremely easily overflows the reaction system to form acidic exhaust gas, particularly in the middle and late stages of the synthesis reaction. However, the overflow problem occurs due to the relatively high price of the high-purity hydrogen chloride, so that raw materials are wasted, and the cost is greatly increased; it also causes pollution and corrosion to the surrounding environment. At present, most of the acidic waste gas is treated by using a mode of absorbing tail gas by alkaline substances. Although the method has good effect, a great amount of three wastes are generated in the treatment process, so that the three-waste treatment burden of a production enterprise is increased, the three-waste treatment cost is high, and the treatment cost also causes great economic burden to the enterprise. Therefore, the development of the tail gas absorption process for producing chloromethyl ethyl ether by an economic, environment-friendly and efficient high-purity hydrogen chloride method has important value and significance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a tail gas absorption process for producing chloromethyl ethyl ether by a high-purity hydrogen chloride method, which aims to solve the problems of more three wastes, large burden of three-waste treatment, higher cost of three-waste treatment and the like in the treatment process in the prior art of absorbing tail gas by adopting alkaline substances.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a tail gas absorption process for producing chloromethyl ethyl ether by a high-purity hydrogen chloride method adopts a device which is completely the same as a main reaction device for producing chloromethyl ethyl ether as a tail gas absorption device;
and the tail gas of the main reaction device is conducted through a pipeline and is introduced into the feed liquid in the tail gas absorption device to carry out tail gas absorption reaction.
Further, in the tail gas absorption reaction process, stirring is carried out, and the temperature of the tail gas absorption device is adjusted to be 20-30 ℃.
Further, the chemical reaction equation of the tail gas absorption is as follows:
further, said C2H5OH: HCL: the molar ratio of HCHO is 1-1.5:1.2: 1.
Further, the tail gas absorption process comprises the following steps:
s001, firstly, adding a predetermined part of ethanol into the main reaction kettle 1, then adding paraformaldehyde in a stirring state, heating and stirring;
and S002, simultaneously in the step S001, adding the same parts of ethanol and polyformaldehyde into the tail gas reaction kettle 2 according to the feeding method in the step S001, heating and stirring.
Further, the tail gas absorption process further comprises the following steps:
s003, after the temperatures in the main reaction kettle 1 and the tail gas reaction kettle 2 are stable, the communication between the reaction kettle 1 and the tail gas reaction kettle 2 and the communication between the tail gas reaction kettle 2 and the tail gas absorption tower 8 are opened;
s004, when the temperature of the main reaction kettle 1 is higher than 10 ℃, introducing high-purity hydrogen chloride gas into the main reaction kettle 1 from a hydrogen chloride steel cylinder 4 through a hydrogen chloride buffer tank 5;
the introducing speed of the high-purity hydrogen chloride gas is 25-35 kg/h.
Further, the tail gas absorption process further comprises the following steps:
s005, after high-purity hydrogen chloride gas is introduced into the main reaction kettle 1, starting a temperature control system of the main reaction kettle 1 when the temperature of the main reaction kettle 1 rises to 25 ℃, and keeping the temperature of the main reaction kettle 1 at 20-30 ℃;
s006, monitoring the temperature of the tail gas reaction kettle 2 in the process of introducing high-purity hydrogen chloride gas into the main reaction kettle 1, and if the temperature of the tail gas reaction kettle 2 exceeds 25 ℃, starting a temperature control system of the tail gas reaction kettle 2 and keeping the temperature of the tail gas reaction kettle 2 at 25-30 ℃.
Further, the tail gas absorption process further comprises the following steps:
s007, after the introduction of the high-purity hydrogen chloride gas is finished, sampling and analyzing the main reaction kettle 1, judging the content of chloromethyl ethyl ether, and performing the following operations according to the content of the chloromethyl ethyl ether:
if the content of the chloromethyl ethyl ether in the product is less than 95 percent, continuously introducing high-purity hydrogen chloride gas for reaction;
if the content of the chloromethyl ethyl ether in the product is more than or equal to 95 percent, stopping introducing high-purity hydrogen chloride gas, keeping the temperature of the main reaction kettle 1 at 15-20 ℃, continuing stirring for 1 hour, standing, and removing a lower-layer water phase; deacidifying the organic phase to obtain chloromethyl ethyl ether product with purity not less than 95%, and transferring the chloromethyl ethyl ether product to a storage kettle 3.
Further, the tail gas absorption process further comprises the following steps:
s008, transferring the materials in the tail gas reaction kettle 2 to a main reaction kettle 1;
repeating the step S002 by the tail gas reaction kettle 2, and adding the ethanol and polyformaldehyde again in the preset parts;
then repeating the steps S003 to S007;
and S009, repeating the step (8).
Further, the temperature of S001 is increased to 10-15 ℃;
stirring at the stirring speed of 60-70 RPM;
and (3) adding paraformaldehyde for several times, wherein the paraformaldehyde is added every 10min, and the adding is finished for five times. Compared with the prior art, the invention has the beneficial effects that:
(1) the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method establishes a process which can utilize a tail gas absorption reaction device which is the same as a main reaction device, can utilize raw materials which are the same as the main reaction device, and can utilize production process conditions which are the same as the main reaction device to carry out tail gas absorption; through the process, the excessive overflowed hydrogen chloride tail gas can be completely absorbed through reaction, and the chloromethyl ethyl ether is generated, so that the aims of eradicating the tail gas, saving raw materials, recycling, reducing the cost and protecting the environment are fulfilled.
(2) According to the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method, through a specific process flow, when the excessive overflowed hydrogen chloride tail gas is completely absorbed, a terminal product, namely chloromethyl ethyl ether, which is the same as that of a main production line can be produced, so that the recycling of waste gas in the production process of the chloromethyl ethyl ether is effectively realized, and the recycling of tail waste resources is effectively realized; after tail gas is absorbed, the conversion rate of the prepared chloromethyl ethyl ether is more than 82 percent, the purity is more than 95 percent, and the method is efficient and stable and can meet the requirements of large-scale and industrial production.
(3) The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method has the same kind of reaction with the main production line, and no side reaction and byproduct are generated in the tail gas absorption process; the special conditions of tail gas leakage, overflow and the like are eliminated, alkali liquor absorption is not needed, the problems of more three wastes, large three-waste treatment burden, higher three-waste treatment cost and the like in the existing tail gas absorption process of alkaline substances are effectively solved, and the tail gas treatment cost is reduced.
(4) The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method can fully recycle the excessive hydrogen chloride by about 15-20 percent, and greatly reduce the production cost of the product.
(5) The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method has the advantages that the yield and the purity of the prepared chloromethyl ethyl ether are high, the product conversion rate and the product quality in the subsequent process are greatly improved when the process is applied to the subsequent process, and the indirect benefit is obvious.
(6) According to the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method, the prepared chloromethyl ethyl ether is used in the synthesis process of chlorfenapyr, and the conversion rate of the chlorfenapyr can be improved by 2-5%.
Drawings
FIG. 1 is a schematic view showing the absorption process of the tail gas from the production of chloromethyl ethyl ether by a high-purity hydrogen chloride process according to the present invention;
in the figure, 1-main reaction kettle; 2-tail gas reaction kettle; 3-a storage kettle; 4-hydrogen chloride steel cylinder; 5-hydrogen chloride buffer tank; 6-tail gas buffer tank; 7-tail gas fan; 8-a tail gas absorption tower; 9-liquid caustic soda tank; 10-tail gas absorption tower circulating pump.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
The utility model provides a tail gas absorption technology of production chloromethyl ethyl ether with high-purity hydrogen chloride method, adopts the device the same with main reaction unit (main reation kettle 1) of production chloromethyl ethyl ether, as tail gas absorbing device (tail gas reation kettle 2), through corrosion-resistant pipeline, will the tail gas of main reaction unit (main reation kettle 1) is introduced to in the feed liquid in tail gas absorbing device (tail gas reation kettle 2), carry out the tail gas absorption reaction.
In the tail gas absorption reaction process, stirring is carried out, and the temperature of the tail gas absorption device (tail gas reaction kettle 2) is adjusted to be 20 ℃.
The tail gas absorption reaction equation is as follows:
the ethanol: hydrogen chloride: the molar ratio of paraformaldehyde is 1.1:1.2:1
The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method comprises the following steps:
(1) adding ethanol in a predetermined part into the main reaction kettle 1, adding paraformaldehyde in several times under stirring, heating to 15 ℃, and stirring.
The ethanol: the total weight ratio of paraformaldehyde is 1.6: 1.
The stirring speed is 63 RPM.
And adding paraformaldehyde for the times, wherein the paraformaldehyde is added every 10min, and the adding is finished for five times.
(2) Meanwhile, the same parts of ethanol and paraformaldehyde are added into the tail gas reaction kettle 2 according to the feeding method in the step (1), the temperature is raised to 20 ℃, and the mixture is stirred.
(3) After the temperature in each reaction kettle is stable, a tail gas absorption tower circulating pump 10, a tail gas fan 7, a tail gas discharge valve from the main reaction kettle 1 to the tail gas reaction kettle 2 and an air inlet valve of the tail gas reaction kettle 2 are sequentially opened.
(4) When the temperature of the main reaction kettle 1 is higher than 10 ℃, slowly opening an air inlet valve of the hydrogen chloride buffer tank 5 and an air outlet valve of the hydrogen chloride steel cylinder 4, adjusting the pressure of the hydrogen chloride buffer tank 5 to 0.2MPa, opening the air outlet valve of the hydrogen chloride buffer tank 5, slowly opening the air inlet valve of the main reaction kettle 1, and introducing high-purity hydrogen chloride gas.
The content of the hydrogen chloride in the high-purity hydrogen chloride gas is more than or equal to 99.5 percent.
The introduction rate of the high-purity hydrogen chloride gas is 30 kg/h.
(5) In the process of introducing high-purity hydrogen chloride gas into the main reaction kettle 1, slowly opening a frozen brine drain valve and a frozen brine inlet valve of the main reaction kettle 1 after the temperature in the kettle rises to 25 ℃; the temperature of the main reaction kettle 1 is kept at 30 ℃ and is not more than 40 ℃ at most.
(6) And monitoring the temperature change of the tail gas reaction kettle 2 in the process of introducing high-purity hydrogen chloride gas into the main reaction kettle 1.
If the temperature of the tail gas reaction kettle 2 exceeds 25 ℃, slowly opening a jacket frozen brine drain valve and a frozen brine inlet valve of the tail gas reaction kettle 2, and keeping the temperature of the tail gas reaction kettle 2 at 30 ℃.
In the tail gas absorption process, the main reaction kettle 1 is in the early stage of the reaction, the concentration of reaction materials is high, most of introduced high-purity hydrogen chloride participates in the reaction, only trace high-purity hydrogen chloride overflows and enters the tail gas reaction kettle 2, and therefore the early-stage temperature change of the tail gas reaction kettle 2 is not large. Meanwhile, the initial reaction temperature of the tail gas reaction kettle 2 is about 18 ℃.
In the tail gas absorption process, the speed of introducing high-purity hydrogen chloride into the main reaction kettle 1 is controlled, and when the total amount of introduced gas is about 60%, the reaction speed in the main reaction kettle 1 starts to gradually decrease along with the gradual decrease of the concentration of the reaction materials in the main reaction kettle 1 according to the chemical reaction balance theory. Therefore, the amount of unreacted hydrogen chloride begins to increase, overflows into the tail gas reaction kettle 2, and reacts with the materials in the tail gas reaction kettle 2. At this time, the concentration of the reaction material in the tail gas reaction vessel 2 is at the maximum, and the hydrogen chloride entering the vessel is added to the material substantially completely.
According to the molar ratio of the materials, even when the reaction is finished, the overflowing amount of the hydrogen chloride is only 20 percent of the theoretical ratio, and almost all the hydrogen chloride participates in the reaction. And it can be seen through the off-gas discharge pipe of the off-gas reaction vessel 2 that almost no gas flows out. The excessive high-purity hydrogen chloride of about 20 percent is almost completely absorbed and is converted into chloromethyl ethyl ether, and only trace high-purity hydrogen chloride enters a tail gas absorption tower 8 through a tail gas discharge pipe, a tail gas buffer tank 6 and a tail gas fan 7 in sequence. Further, a pipeline at the lower end of the tail gas absorption tower 8 is connected with a liquid caustic soda tank 9, and liquid caustic soda circulating spraying is carried out through a circulating pump 10 of the tail gas absorption tower.
(7) After the introduction of the high-purity hydrogen chloride gas is finished, sampling the main reaction kettle 1 to analyze the content of chloromethyl ethyl ether, and performing the following operations according to the content of the chloromethyl ethyl ether:
a. if the content of the chloromethyl ethyl ether is less than 95 percent, continuously introducing 5 percent of high-purity hydrogen chloride for reaction, sampling again to analyze the content of the chloromethyl ethyl ether, and carrying out a or b treatment according to the content of the chloromethyl ethyl ether.
b. If the content of the chloromethyl ethyl ether in the product is more than or equal to 95 percent, stopping introducing the hydrogen chloride, keeping the temperature at 20 ℃, continuing stirring for 1 hour, standing, and removing the water in the lower layer; then deacidifying to obtain chloromethyl ethyl ether product with purity not less than 95%; and the chloromethyl ethyl ether product was transferred to storage vessel 3.
(8) The tail gas reaction kettle 2 absorbs about 20% of high-purity hydrogen chloride overflowing from the main reaction kettle 1, and materials in the tail gas reaction kettle 2 are changed into homogeneous liquid from suspension; transferring the materials in the tail gas reaction kettle 2 into a main reaction kettle 1; the tail gas reaction kettle 2 repeats the step (2), and ethanol and polyformaldehyde with preset parts are added again; repeating the steps (3) to (7); the tail gas reaction kettle 2 absorbs the high-purity hydrogen chloride overflowing from the main reaction kettle 1 again.
(9) And (5) repeating the step (8).
The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment establishes a process which can utilize a tail gas absorption reaction device which is the same as a main reaction device, can utilize raw materials which are the same as the main reaction device, and can utilize production process conditions which are the same as the main reaction device to carry out tail gas absorption; by the process, the excessive overflowing hydrogen chloride tail gas can be completely absorbed through reaction, and the chloromethyl ethyl ether is generated.
Furthermore, through a specific process flow, the excessive overflowed hydrogen chloride tail gas is completely absorbed, and simultaneously, the same terminal product, namely chloromethyl ethyl ether, as the main production line can be produced, so that the cyclic reuse of waste gas in the production process of the chloromethyl ethyl ether is effectively realized. Meanwhile, after tail gas is absorbed, the conversion rate of the prepared chloromethyl ethyl ether is 85.2 percent, the purity is 96.7 percent, and the method is efficient and stable and can meet the requirements of large-scale and industrial production.
Furthermore, the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment has the same reaction with the main production line, and no side reaction and byproduct are generated in the tail gas absorption process; alkali liquor absorption is not needed, and the tail gas treatment cost is reduced.
Further, the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment can fully recycle about 20% of excessive hydrogen chloride; the prepared chloromethyl ethyl ether is applied to the subsequent synthesis process of the chlorfenapyr, the product conversion rate and the quality of the subsequent process are greatly improved, wherein the conversion rate of the chlorfenapyr can be improved by about 5 percent.
Example 2
The utility model provides a tail gas absorption technology of production chloromethyl ethyl ether with high-purity hydrogen chloride method, adopts the device the same with main reaction unit (main reation kettle 1) of production chloromethyl ethyl ether, as tail gas absorbing device (tail gas reation kettle 2), through corrosion-resistant pipeline, will the tail gas of main reaction unit (main reation kettle 1) is introduced to in the feed liquid in tail gas absorbing device (tail gas reation kettle 2), carry out the tail gas absorption reaction.
In the tail gas absorption reaction process, stirring is carried out, and the temperature of the tail gas absorption device (tail gas reaction kettle 2) is adjusted to 23 ℃.
The tail gas absorption reaction equation is as follows:
the ethanol: hydrogen chloride: the molar ratio of paraformaldehyde is 1.5:1.2: 1.
The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method comprises the following steps:
(1) adding ethanol in a predetermined part into the main reaction kettle 1, adding paraformaldehyde in several times under stirring, heating to 12 ℃, and stirring.
The ethanol: the total weight ratio of paraformaldehyde is 1.6: 1.
The stirring speed is 70 RPM.
And adding paraformaldehyde for the times, wherein the paraformaldehyde is added every 10min, and the adding is finished for five times.
(2) Meanwhile, the same parts of ethanol and paraformaldehyde are added into the tail gas reaction kettle 2 according to the feeding method in the step (1), the temperature is raised to 23 ℃, and the mixture is stirred.
(3) After the temperature in each reaction kettle is stable, a tail gas absorption tower circulating pump 10, a tail gas fan 7, a tail gas discharge valve from the main reaction kettle 1 to the tail gas reaction kettle 2 and an air inlet valve of the tail gas reaction kettle 2 are sequentially opened.
(4) When the temperature of the main reaction kettle 1 is higher than 10 ℃, slowly opening an air inlet valve of the hydrogen chloride buffer tank 5 and an air outlet valve of the hydrogen chloride steel cylinder 4, adjusting the pressure of the hydrogen chloride buffer tank 4 to 0.2MPa, opening the air outlet valve of the hydrogen chloride buffer tank 5, slowly opening the air inlet valve of the main reaction kettle 1, and introducing high-purity hydrogen chloride gas.
The content of the hydrogen chloride in the high-purity hydrogen chloride gas is more than or equal to 99.5 percent.
The introduction rate of the high-purity hydrogen chloride gas is 32 kg/h.
(5) After high-purity hydrogen chloride gas is introduced into the main reaction kettle 1, slowly opening a frozen brine drain valve and a frozen brine inlet valve of the main reaction kettle 1 after the temperature is raised to 25 ℃; the temperature of the main reaction kettle 1 is kept at 25 ℃.
(6) And monitoring the temperature change of the tail gas reaction kettle 2 in the process of introducing high-purity hydrogen chloride gas into the main reaction kettle 1.
If the temperature of the tail gas reaction kettle 2 exceeds 25 ℃, slowly opening a jacket frozen brine drain valve and a frozen brine inlet valve of the tail gas reaction kettle 2, and keeping the temperature of the tail gas reaction kettle 2 at 25 ℃.
In the tail gas absorption process, the main reaction kettle 1 is in the early stage of the reaction, the concentration of reaction materials is high, most of introduced high-purity hydrogen chloride participates in the reaction, only trace high-purity hydrogen chloride overflows and enters the tail gas reaction kettle 2, and therefore the early-stage temperature change of the tail gas reaction kettle 2 is not large. Meanwhile, the initial reaction temperature of the tail gas reaction kettle 2 is about 18 ℃.
In the tail gas absorption process, the speed of introducing high-purity hydrogen chloride into the main reaction kettle 1 is controlled, and when the total amount of introduced gas is about 60%, the reaction speed in the main reaction kettle 1 starts to gradually decrease along with the gradual decrease of the concentration of the reaction materials in the main reaction kettle 1 according to the chemical reaction balance theory. Therefore, the amount of unreacted hydrogen chloride begins to increase, overflows into the tail gas reaction kettle 2, and reacts with the materials in the tail gas reaction kettle 2. At this time, the concentration of the reaction material in the tail gas reaction vessel 2 is at the maximum, and the hydrogen chloride entering the vessel is added to the material substantially completely.
According to the molar ratio of the materials, even when the reaction is finished, the overflowing amount of the hydrogen chloride is only 20 percent of the theoretical ratio, and almost all the hydrogen chloride participates in the reaction. And it can be seen through the off-gas discharge pipe of the off-gas reaction vessel 2 that almost no gas flows out. The excessive high-purity hydrogen chloride of about 20 percent is almost completely absorbed and is converted into chloromethyl ethyl ether, and only trace high-purity hydrogen chloride enters a tail gas absorption tower 8 through a tail gas discharge pipe, a tail gas buffer tank 6 and a tail gas fan 7 in sequence. Further, a pipeline at the lower end of the tail gas absorption tower 8 is connected with a liquid caustic soda tank 9, and liquid caustic soda circulating spraying is carried out through a circulating pump 10 of the tail gas absorption tower.
(7) After the introduction of the high-purity hydrogen chloride gas is finished, sampling the main reaction kettle 1 to analyze the content of chloromethyl ethyl ether, and performing the following operations according to the content of the chloromethyl ethyl ether:
a. if the content of the chloromethyl ethyl ether is less than 95 percent, continuously introducing 5 percent of high-purity hydrogen chloride for reaction, sampling again to analyze the content of the chloromethyl ethyl ether, and carrying out a or b treatment according to the content of the chloromethyl ethyl ether.
b. If the content of the chloromethyl ethyl ether in the product is more than or equal to 95 percent, stopping introducing the hydrogen chloride, keeping the temperature at 20 ℃, continuing stirring for 1 hour, standing, and removing the water in the lower layer; then deacidifying to obtain chloromethyl ethyl ether product with purity not less than 95%; and the chloromethyl ethyl ether product was transferred to storage vessel 3.
(8) The tail gas reaction kettle 2 absorbs about 20% of high-purity hydrogen chloride overflowing from the main reaction kettle 1, and materials in the tail gas reaction kettle 2 are changed into homogeneous liquid from suspension; transferring the materials in the tail gas reaction kettle 2 into a main reaction kettle 1; the tail gas reaction kettle 2 repeats the step (2), and ethanol and polyformaldehyde with preset parts are added again; repeating the steps (3) to (7); the tail gas reaction kettle 2 absorbs the high-purity hydrogen chloride overflowing from the main reaction kettle 1 again.
(9) And (5) repeating the step (8).
The tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment establishes a process which can utilize a tail gas absorption reaction device which is the same as a main reaction device, can utilize raw materials which are the same as the main reaction device, and can utilize production process conditions which are the same as the main reaction device to carry out tail gas absorption; by the process, the excessive overflowing hydrogen chloride tail gas can be completely absorbed through reaction, and the chloromethyl ethyl ether is generated.
Furthermore, through a specific process flow, the excessive overflowed hydrogen chloride tail gas is completely absorbed, and simultaneously, the same terminal product, namely chloromethyl ethyl ether, as the main production line can be produced, so that the cyclic reuse of waste gas in the production process of the chloromethyl ethyl ether is effectively realized. Meanwhile, after tail gas is absorbed, the prepared chloromethyl ethyl ether has the conversion rate of 83.5 percent and the purity of 95.3 percent, is efficient and stable, and can meet the requirements of large-scale and industrial production.
Furthermore, the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment has the same reaction with the main production line, and no side reaction and byproduct are generated in the tail gas absorption process; alkali liquor absorption is not needed, and the tail gas treatment cost is reduced.
Further, the tail gas absorption process for producing chloromethyl ethyl ether by using the high-purity hydrogen chloride method of the embodiment can fully recycle about 20% of excessive hydrogen chloride; the prepared chloromethyl ethyl ether is applied to the subsequent synthesis process of the chlorfenapyr, the product conversion rate and the quality of the subsequent process are greatly improved, wherein the conversion rate of the chlorfenapyr can be improved by about 2 percent.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A tail gas absorption process for producing chloromethyl ethyl ether by a high-purity hydrogen chloride method is characterized in that a device which is completely the same as a main reaction device for producing chloromethyl ethyl ether is adopted as a tail gas absorption device;
and the tail gas of the main reaction device is conducted through a pipeline and is introduced into the feed liquid in the tail gas absorption device to carry out tail gas absorption reaction.
2. The process for absorbing tail gas generated in the production of chloromethyl ethyl ether by the high-purity hydrogen chloride process according to claim 1, wherein the tail gas absorbing reaction is carried out while stirring, and the temperature of the tail gas absorbing device is adjusted to 20-30 ℃.
3. The tail gas absorption process for producing chloromethyl ethyl ether by the high-purity hydrogen chloride process according to claim 1, characterized in that the chemical reaction equation of the tail gas absorption is as follows:
4. the process for absorbing tail gas generated in the production of chloromethyl ethyl ether by high-purity hydrogen chloride process according to claim 3, characterized in that C is2H5OH: HCL: the molar ratio of HCHO is 1-1.5:1.2: 1.
5. The tail gas absorption process for producing chloromethyl ethyl ether by the high-purity hydrogen chloride method according to claim 1, characterized in that the tail gas absorption process comprises the following steps:
s001, firstly, adding a predetermined part of ethanol into the main reaction kettle 1, then adding paraformaldehyde in a stirring state, heating and stirring;
and S002, simultaneously in the step S001, adding the same parts of ethanol and polyformaldehyde into the tail gas reaction kettle 2 according to the feeding method in the step S001, heating and stirring.
6. The tail gas absorption process for producing chloromethyl ethyl ether according to the high-purity hydrogen chloride method of claim 5, characterized in that the tail gas absorption process further comprises the following steps:
s003, after the temperatures in the main reaction kettle 1 and the tail gas reaction kettle 2 are stable, the communication between the reaction kettle 1 and the tail gas reaction kettle 2 and the communication between the tail gas reaction kettle 2 and the tail gas absorption tower 8 are opened;
s004, when the temperature of the main reaction kettle 1 is higher than 10 ℃, introducing high-purity hydrogen chloride gas into the main reaction kettle 1 from a hydrogen chloride steel cylinder 4 through a hydrogen chloride buffer tank 5;
the introducing speed of the high-purity hydrogen chloride gas is 25-35 kg/h.
7. The tail gas absorption process for producing chloromethyl ethyl ether according to the high-purity hydrogen chloride method of claim 6, characterized in that the tail gas absorption process further comprises the following steps:
s005, after high-purity hydrogen chloride gas is introduced into the main reaction kettle 1, starting a temperature control system of the main reaction kettle 1 when the temperature of the main reaction kettle 1 rises to 25 ℃, and keeping the temperature of the main reaction kettle 1 at 20-30 ℃;
s006, monitoring the temperature of the tail gas reaction kettle 2 in the process of introducing high-purity hydrogen chloride gas into the main reaction kettle 1, and if the temperature of the tail gas reaction kettle 2 exceeds 25 ℃, starting a temperature control system of the tail gas reaction kettle 2 and keeping the temperature of the tail gas reaction kettle 2 at 25-30 ℃.
8. The tail gas absorption process for producing chloromethyl ethyl ether by the high-purity hydrogen chloride method according to claim 7, characterized in that the tail gas absorption process further comprises the following steps:
s007, after the introduction of the high-purity hydrogen chloride gas is finished, sampling the main reaction kettle 1 to analyze the content of chloromethyl ethyl ether in the product, and performing the following operations according to the content of the chloromethyl ethyl ether:
a. if the content of the chloromethyl ethyl ether is less than 95 percent, continuously introducing 5 percent of high-purity hydrogen chloride for reaction, sampling again to analyze the content of the chloromethyl ethyl ether, and carrying out a or b treatment according to the content of the chloromethyl ethyl ether;
b. if the content of the chloromethyl ethyl ether in the product is more than or equal to 95 percent, stopping introducing high-purity hydrogen chloride gas, keeping the temperature of the main reaction kettle 1 at 15-20 ℃, continuing stirring for 1 hour, standing, and removing a lower-layer water phase; deacidifying the organic phase to obtain chloromethyl ethyl ether product with purity not less than 95%, and transferring the chloromethyl ethyl ether product to a storage kettle 3.
9. The tail gas absorption process for producing chloromethyl ethyl ether according to the high-purity hydrogen chloride method of claim 8, characterized in that the tail gas absorption process further comprises the following steps:
s008, transferring the materials in the tail gas reaction kettle 2 to a main reaction kettle 1;
repeating the step S002 by the tail gas reaction kettle 2, and adding the ethanol and polyformaldehyde again in the preset parts;
then repeating the steps S003 to S007;
and S009, repeating the step (8).
10. The tail gas absorption process for producing chloromethyl ethyl ether according to the high-purity hydrogen chloride method of claim 5, characterized in that the temperature of S001 is raised to 10-15 ℃;
stirring at the stirring speed of 60-70 RPM;
and (3) adding paraformaldehyde for several times, wherein the paraformaldehyde is added every 10min, and the adding is finished for five times.
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