CN112961132A - Method for preparing monochlorophthalic anhydride in micro-channel continuous flow reactor - Google Patents
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Abstract
The invention relates to the technical field of organic synthesis application, in particular to a method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor; the method comprises the following steps: A. respectively introducing soluble phthalate solution and chlorine into a preheating module a and a preheating module b of the micro-channel continuous flow reactor for preheating; B. sending the preheated phthalate solution and chlorine into a mixing module of a micro-channel continuous flow reactor for mixing, then entering a reaction module for carrying out chlorination reaction, and adjusting the reaction pressure to be 0.1-1.8MPa and the reaction temperature to be 10-200 ℃; C. feeding the metered alkali solution into the reaction module in the step B; D. c, pumping the reaction liquid obtained in the step C into a cooling module, and then passing through a gas-liquid separation module, an acidification unit, a dehydration unit and a separation unit to obtain monochlorophthalic anhydride; the method has the advantages of short reaction time, good product selectivity, mild reaction conditions, high yield, safe reaction process and improved practicability.
Description
Technical Field
The invention relates to the technical field of organic synthesis application, in particular to a method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor.
Background
The monochlorophthalic anhydride is an important chemical raw material, is widely applied in the fields of medicines, pesticides, plastics, dyes and the like, can be used as a plant growth promoter, can be used for preparing an antioxidant and an anti-tumor drug, can also be used for preparing an important intermediate of biphenyl tetracarboxylic dianhydride to further prepare polyimide, and is a fine organic chemical product with high added value.
At present, the industrial production of monochlorophthalic anhydride still adopts the traditional kettle type mechanical stirring reactor, the heat transfer rate of the reactor is slow, the gas-liquid contact area is small, the material mixing is not uniform, the byproduct is high, and the reaction efficiency is low.
The microchannel reactor has unique structural characteristics, so that the heat transfer efficiency and the mass transfer efficiency of the microchannel reactor are higher than those of the traditional kettle type reactor, the reaction time can be shortened, the occurrence of side reactions is reduced, and the flexibility and the safety of production can be improved.
Chinese patent CN109438219A discloses a method for preparing monochlorophthalic anhydride by using a microchannel reactor, but the reactant feeding amount is too low and there is no industrial production value; chinese patent CN 108997284 a discloses a method for producing monochlorobenzoic anhydride by using chloro-o-xylene as raw material, acetic acid as solvent, cobalt-manganese-bromine as catalyst and micro-channel reactor, which has certain environmental problems due to the use of liquid phase cobalt salt and manganese salt. Chinese patent CN 1526710A discloses a preparation method of 4-chlorophthalic anhydride, which adopts a stirred tank reactor, the mass yield of the 4-chlorophthalic anhydride is 50-60%, and the product yield is lower.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor, which has the advantages of short reaction time, good product selectivity, mild reaction conditions, high yield, safe reaction process and improved practicability.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor, comprising the steps of:
A. respectively introducing soluble phthalate solution and chlorine into a preheating module a and a preheating module b of the micro-channel continuous flow reactor for preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module of a micro-channel continuous flow reactor for mixing, then entering a reaction module for carrying out chlorination reaction, and adjusting the reaction pressure to be 0.1-1.8MPa and the reaction temperature to be 10-200 ℃;
C. feeding the metered alkali solution into the reaction module in the step B;
D. and D, pumping the reaction liquid obtained in the step C into a cooling module, and then passing through a gas-liquid separation module, an acidification unit, a dehydration unit and a separation unit to obtain monochlorophthalic anhydride.
Preferably, in the step A, the heating temperature of the preheating module a and the preheating module b is 10-180 ℃.
Preferably, in the step B, the temperature of the mixing reaction module is 10-180 ℃.
Preferably, in the step C, the alkali solution may be added through one inlet in the reaction module, or may be simultaneously added through a plurality of inlets in the reaction module.
Preferably, in the step C, the alkali solution is one or more of sodium hydroxide, potassium hydroxide and sodium carbonate.
Preferably, in the step D, the cooling temperature is-20 to 30 ℃.
Preferably, in the step a, the molar ratio of the phthalate to the chlorine is 1: 0.6-3.
Preferably, in the step D, hydrochloric acid and sulfuric acid are adopted in the operation of the acidification unit; in the operation of the dehydration unit, toluene or xylene as a water-carrying agent can be added and heated for dehydration.
Preferably, in the step D, the separation unit operation is hot filtration, centrifugation or rectification.
A micro-channel continuous flow reactor for preparing monochlorophthalic anhydride comprises a preheating module a, a preheating module b, a mixing module, a reaction module, a cooling module, a gas-liquid separation module, a tail gas absorption unit, an acidification unit, a dehydration unit and a separation unit.
(III) advantageous effects
Compared with the prior art, the invention provides a method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor, which has the following beneficial effects:
1. the method for preparing monochlorophthalic anhydride in the micro-channel continuous flow reactor has the advantages that the conversion rate of raw materials is high, the conversion rate of phthalic anhydride is 73.5-99.4%, and the mass yield of the total monochlorophthalic anhydride is 75.8-115.6%;
2. according to the method for preparing monochlorophthalic anhydride in the micro-channel continuous flow reactor, the chlorination reaction time can be shortened from several hours of a kettle type reactor to dozens of seconds to several minutes, continuous production is realized, and the production cost is reduced.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
FIG. 2 is a schematic view of a microchannel reactor channel configuration of the present invention;
FIG. 3 is a schematic view of another configuration of a microchannel reactor channel of the present invention;
in the drawings, the reference numbers: 1. a preheating module a; 2. a preheating module b; 3. a mixing module; 4. a reaction module; 5. a cooling module; 6. a gas-liquid separation module; 7. tail gas absorption; 8. an acidification unit; 9. a dehydration unit; 10. a separation unit.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
referring to fig. 1, a method of the present invention for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprises the steps of:
A. respectively introducing soluble monosodium phthalate solution and chlorine gas into a preheating module a1 and a preheating module b2 of the micro-channel continuous flow reactor according to the molar ratio of 1:0.9, and preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module 3 of a micro-channel continuous flow reactor for mixing, then entering a reaction module 4 for carrying out chlorination reaction, and adjusting the reaction pressure to be 0.5MPa and the reaction temperature to be 70 ℃;
C. feeding the metered alkali solution into the reaction module 4 in the step B;
D. c, pumping the reaction liquid obtained in the step C into a cooling module 5, cooling to 20 ℃, and then passing through a gas-liquid separation module 6, an acidification unit 8, a hydrochloric acid acidification and dehydration unit 9 and a separation unit 10 to obtain monochlorophthalic anhydride; the total mass yield of monochlorophthalic anhydride is 86.87%, and the conversion rate of phthalic anhydride is 75.28%.
Example 2:
referring to fig. 1, a method of the present invention for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprises the steps of:
A. respectively introducing soluble monosodium phthalate solution and chlorine gas into a preheating module a1 and a preheating module b2 of the micro-channel continuous flow reactor according to the molar ratio of 1:2.8, and preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module 3 of a micro-channel continuous flow reactor for mixing, then entering a reaction module 4 for carrying out chlorination reaction, and adjusting the reaction pressure to be 1.2MPa and the reaction temperature to be 95 ℃;
C. feeding the metered alkali solution into the reaction module 4 in the step B;
D. c, pumping the reaction liquid obtained in the step C into a cooling module 5, cooling to 10 ℃, and then performing hydrochloric acid acidification by a gas-liquid separation module 6 and an acidification unit 8, a dehydration unit 9 and a separation unit 10 to obtain monochlorophthalic anhydride; the total mass yield of the monochlorophthalic anhydride is 78.26 percent, and the conversion rate of the phthalic anhydride is 98.36 percent;
example 3:
referring to fig. 1, a method of the present invention for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprises the steps of:
A. respectively introducing soluble monosodium phthalate solution and chlorine gas into a preheating module a1 and a preheating module b2 of the micro-channel continuous flow reactor according to the molar ratio of 1:1.10, and preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module 3 of a micro-channel continuous flow reactor for mixing, then entering a reaction module 4 for carrying out chlorination reaction, and adjusting the reaction pressure to be 1.2MPa and the reaction temperature to be 120 ℃;
C. feeding the metered alkali solution into the reaction module 4 in the step B;
D. c, pumping the reaction liquid obtained in the step C into a cooling module 5, cooling to 10 ℃, and then performing hydrochloric acid acidification by a gas-liquid separation module 6 and an acidification unit 8, a dehydration unit 9 and a separation unit 10 to obtain monochlorophthalic anhydride; the total mass yield of the monochlorophthalic anhydride is 95.66 percent, and the conversion rate of the phthalic anhydride is 88.57 percent;
example 4:
referring to fig. 1, a method of the present invention for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprises the steps of:
A. respectively introducing soluble monosodium phthalate solution and chlorine gas into a preheating module a1 and a preheating module b2 of the micro-channel continuous flow reactor according to the molar ratio of 1:1.03 for preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module 3 of a micro-channel continuous flow reactor for mixing, then entering a reaction module 4 for carrying out chlorination reaction, and adjusting the reaction pressure to be 1.5MPa and the reaction temperature to be 150 ℃;
C. feeding the metered alkali solution into the reaction module 4 in the step B;
D. c, pumping the reaction liquid obtained in the step C into a cooling module 5, cooling to 15 ℃, and then passing through a gas-liquid separation module 6, an acidification unit 8, a hydrochloric acid acidification and dehydration unit 9 and a separation unit 10 to obtain monochlorophthalic anhydride; the total mass yield of the monochlorophthalic anhydride is 112.09 percent, and the conversion rate of the phthalic anhydride is 97.14 percent;
example 5:
referring to fig. 1, a method of the present invention for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprises the steps of:
A. respectively introducing soluble monosodium phthalate solution and chlorine gas into a preheating module a1 and a preheating module b2 of the micro-channel continuous flow reactor according to the molar ratio of 1:0.95, and preheating;
B. sending the preheated phthalate solution and chlorine into a mixing module 3 of a micro-channel continuous flow reactor for mixing, then entering a reaction module 4 for carrying out chlorination reaction, and adjusting the reaction pressure to be 0.2MPa and the reaction temperature to be 50 ℃;
C. feeding the metered alkali solution into the reaction module 4 in the step B;
D. c, pumping the reaction liquid obtained in the step C into a cooling module 5, cooling to 15 ℃, and then passing through a gas-liquid separation module 6, an acidification unit 8, a hydrochloric acid acidification and dehydration unit 9 and a separation unit 10 to obtain monochlorophthalic anhydride; the total mass yield of the monochlorophthalic anhydride is 82.74 percent, and the conversion rate of the phthalic anhydride is 70.33 percent;
referring to fig. 2 and 3, a micro-channel continuous flow reactor for preparing monochlorophthalic anhydride comprises a preheating module a1, a preheating module b2, a mixing module 3, a reaction module 4, a temperature reduction module 5, a gas-liquid separation module 6, a tail gas absorption 7, an acidification unit 8, a dehydration unit 9 and a separation unit 10;
compared with the prior art, the invention has the following remarkable characteristics: the conversion rate of the raw materials is high, the conversion rate of phthalic anhydride is 73.5-99.4%, and the mass yield of the total monochlorophthalic anhydride is 75.8-115.6%; the chlorination reaction time can be shortened from several hours of the kettle type reactor to dozens of seconds to several minutes, thereby realizing continuous production and reducing the production cost.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A process for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor comprising the steps of:
A. respectively introducing soluble phthalate solution and chlorine into a preheating module a (1) and a preheating module b (2) of the micro-channel continuous flow reactor for preheating;
B. sending the preheated phthalate solution and chlorine gas into a mixing module (3) of a micro-channel continuous flow reactor for mixing, then entering a reaction module (4) for starting chlorination reaction, and adjusting the reaction pressure to be 0.1-1.8MPa and the reaction temperature to be 10-200 ℃;
C. feeding a metered alkali solution into the reaction module (4) in step B;
D. and C, pumping the reaction liquid obtained in the step C into a cooling module (5), and then passing through a gas-liquid separation module (6), an acidification unit (8), a dehydration unit (9) and a separation unit (10) to obtain monochlorophthalic anhydride.
2. The method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor according to claim 1, wherein the heating temperature of the preheating module a (1) and the preheating module b (2) in the step a is 10-180 ℃.
3. The method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor according to claim 1, wherein the temperature of the mixing reaction module (4) in step B is 10 to 180 ℃.
4. The process for the preparation of monochlorophthalic anhydride in a microchannel continuous flow reactor as set forth in claim 1, wherein said base solution is introduced through one inlet of reaction block (4) or simultaneously through multiple inlets of reaction block (4) in step C.
5. The method for preparing monochlorophthalic anhydride in a microchannel continuous flow reactor as recited in claim 1, wherein in step C, the base solution is one or more of sodium hydroxide, potassium hydroxide, and sodium carbonate.
6. The method for preparing monochlorophthalic anhydride in a micro-channel continuous flow reactor as claimed in claim 1, wherein the cooling temperature in step D is-20 to 30 ℃.
7. The process of claim 1 wherein in step a, the molar ratio of phthalate to chlorine is from 1: 0.6-3.
8. The process for the preparation of monochlorophthalic anhydride in a microchannel continuous flow reactor as set forth in claim 1 wherein, in step D, hydrochloric acid and sulfuric acid are employed in the operation of the acidification unit (8); in the operation of the dehydration unit (9), toluene or xylene as a water-carrying agent can be added and heated for dehydration.
9. The process for the preparation of monochlorophthalic anhydride in a microchannel continuous flow reactor according to claim 1, characterized in that in step D the separation unit (10) is operated with hot filtration, centrifugation or rectification.
10. A micro-channel continuous flow reactor for use in the method of producing monochlorophthalic anhydride according to any one of claims 1 to 9, characterized by comprising a preheating module a (1), a preheating module b (2), a mixing module (3), a reaction module (4), a temperature reduction module (5), a gas-liquid separation module (6), a tail gas absorption (7), an acidification unit (8), a dehydration unit (9) and a separation unit (10).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563291A (en) * | 2021-08-03 | 2021-10-29 | 哈尔滨工业大学（威海） | Novel method for preparing chlorophthalic anhydride by solvent-free catalytic oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526710A (en) * | 2003-09-25 | 2004-09-08 | 华东师范大学 | Prepn of 4-chlorophthalic anhydride |
| CN108752161A (en) * | 2018-07-16 | 2018-11-06 | 山东冠森高分子材料科技股份有限公司 | The method of synthesis of alpha-single chloro ortho-xylene in continuous flow micro passage reaction |
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2021
- 2021-02-24 CN CN202110204911.6A patent/CN112961132A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526710A (en) * | 2003-09-25 | 2004-09-08 | 华东师范大学 | Prepn of 4-chlorophthalic anhydride |
| CN108752161A (en) * | 2018-07-16 | 2018-11-06 | 山东冠森高分子材料科技股份有限公司 | The method of synthesis of alpha-single chloro ortho-xylene in continuous flow micro passage reaction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563291A (en) * | 2021-08-03 | 2021-10-29 | 哈尔滨工业大学（威海） | Novel method for preparing chlorophthalic anhydride by solvent-free catalytic oxidation |
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