CN103570018A - Safe phosgene preparation method and device - Google Patents

Safe phosgene preparation method and device Download PDF

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Publication number
CN103570018A
CN103570018A CN201310516134.4A CN201310516134A CN103570018A CN 103570018 A CN103570018 A CN 103570018A CN 201310516134 A CN201310516134 A CN 201310516134A CN 103570018 A CN103570018 A CN 103570018A
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phosgene
micro
passage reaction
reaction
micro passage
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胡万鹏
周兴贵
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East China University of Science and Technology
Jiaxing University
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East China University of Science and Technology
Jiaxing University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Abstract

The invention provides a process and a device for safely preparing phosgene. The synthetic process adopts carbon tetrachloride and a hydrogen peroxide solution as raw materials, the raw materials are mixed in a miniature mixer in a strengthening manner under the action of a catalyzer and then enter micro-channel reactors to continue to react so as to generate the phosgene; on-line normal position conversion is adopted to consume the phosgene, immersion absorption is adopted to prevent the phosgene from leaking, and the miniature mixer, a first micro-channel reactor and a second micro-channel reactor are all arranged in a constant temperature bath. A synthesizer comprises a first constant flow pump, a second constant flow pump, a third constant flow pump, the miniature mixer, the first micro-channel reactor, the second micro-channel reactor, a product receiver and the constant temperature bath. The method provided by the invention has the advantages that the reaction condition is gentle, the reaction time is short, and the reaction conversion rate and the selectivity are good. The device provided by the invention has the advantages that the design is simple, the productive process is airtight and continuous, and the dangerousness in the production and storage is reduced.

Description

A kind of safe phosgene manufacturing process and device
Technical field
The invention belongs to field of chemical engineering, relate to a kind of safe preparation method of hazardous chemical, relate in particular to the safe preparation method of phosgene under laboratory condition.
Background technology
Phosgene, has another name called carbonyl chloride, CAS No:75-44-5, there is active chemical property, because its molecule can provide carbonyl functional group, be widely used among organic synthesis, in agricultural chemicals, medicine, macromolecular material and biochemical product etc. synthetic, be important basic industry raw material.But phosgene sucks people's cognition and causes pulmonary edema dead, is therefore a kind of hypertoxicity gas.Its boiling point is low, volatility is large, and danger is also larger.
Existing phosgene synthesis technique is to use hypertoxic chlorine (Cl 2) and carbon monoxide (CO) gas phase catalytic reaction under the effect of gac produce, adopt shell and tube or bundle pipe type reactor, temperature of reaction is up to 200～300 oC.Because the capacity of heat transmission of carbon-coating is not high, cause the thermal insulation warming of reactor larger.Any leakage of reaction unit and pipeline, all may make it to become " gas bomb " of not timing.
The technology that the microreactor of having reported is prepared phosgene is that existing industrial technology is microminiaturized, in the inwall coating activated carbon granule coating of microreactor, passes into the chlorine (Cl of microreactor 2) and carbon monoxide (CO) synthetic phosgene under the katalysis of activated carbon coating.This technology is not still avoided the leakage hidden danger of raw material poison gas.
Russian scientist adopts to CCl 4the method that drips hydrogen peroxide is produced phosgene, and the catalyzer of employing is anhydrous FeCl 3powder, the method adopts cold-trap to collect the phosgene that reaction produces.The method gas production rate is little, but still can not solve the difficult problem that phosgene leaks completely, brings difficulty to the use of phosgene.
Tetracol phenixin (CCl 4, the by product reacting while CTC) being methane chlorination production methyl chloride.Because tetracol phenixin (CTC) is a kind of material damaging the ozone layer (ODS), according to the relevant regulations of the Montreal Protocol > > of < < Ozone Depleting Substances and the superseded national scheme of Chinese ODS, China will cut down CCl by the superseded mode of industry 4consumption, develop CCl 4technology be a urgent problem.
Summary of the invention
The object of the invention is take tetracol phenixin as raw material, the phosgene technology of preparing that exploitation is clean, safe, is transformed into tetracol phenixin and has the more industrial raw material of high added value; Produce as required, need not store, eliminate phosgene and store the danger of bringing, avoid the waste of losing efficacy and causing because storing.
The present invention will solve is storage, transportation and the use inconvenience existing in traditional phosgene manufacturing process, can not solve the defect that phosgene leaks completely.
The security advantages that micro passage reaction is prepared hazardous chemical is that in reactor, liquid holdup is little, and microchannel load performance is good, is difficult for leaking.The present invention adopts microreactor technology to prepare phosgene, and another raw material of use is aqueous hydrogen peroxide solution, is also a kind of industrial chemicals of clean environment firendly.Micro mixer is strengthened both reaction mass mixing processes, and phosgene produces and realize online converted in-situ in microchannel, and the generation of phosgene and flow is all carried out in withstand voltage stainless steel microchannel, can not leak.Therefore, the present invention is the Technology of preparing a kind of safety and environmental protection of phosgene.
The reaction principle the present invention relates to is:
2CCl 4 ＋ 2H 2O 2
Figure 888130DEST_PATH_IMAGE001
2COCl 2 ＋ 4HCl ＋ O 2 （1）
CCl 4 ＋ H 2O COCl 2 ＋ 2HCl （2）
COCl 2 ＋ 4NH 3 → CO(NH 2) 2 ＋ 2NH 4Cl （3）
Technique provided by the invention at least comprises the following steps: by the low-carbon alcohol solution that contains tetracol phenixin, catalyzer and certain density superoxol, by two constant flow pumps, be injected in micro mixer respectively, owing to existing micron-sized runner in micro mixer, feed liquid " is dissectd " as micron-sized drop, and being conducive to material carries out mass transfer by molecular diffusion form; Enter the tetracol phenixin in micro mixer, the low-carbon alcohol solution of catalyzer mixes at micro mixer inner impact with superoxol, feed liquid obtains very high Reynolds number, mixed effect is strengthened greatly; Then mixing solutions flows in micro passage reaction and carries out catalytic oxidation, generates phosgene; End collecting reaction product at the second micro passage reaction; Described phosgene preparation technology adopts the method for converted in-situ to consume phosgene; Described phosgene preparation technology adopts the mode of Tritium Immersion Absorption to prevent phosgene leakage; Described micro mixer and first, second micro passage reaction are all placed in thermostatic bath.
The concentration of described tetracol phenixin is 5～100 g/L; Described low-carbon alcohol is ethanol.
Described catalyzer is Anhydrous Ferric Chloride; The concentration of described catalyzer is 5～50 g/L.
In described reaction process, the temperature range of thermostatic bath is controlled between 20～80 oC.
The material adopting in described converted in-situ method is ammoniacal liquor.
In described preparation technology, whole reaction unit is immersed in basic solution; Described basic solution is a kind of in weak ammonia or sodium hydroxide solution.
In described reaction process, the volumetric flow rate scope of tetracol phenixin, catalyst solution and superoxol is 1.0～20 mL/min.
The device that safety of the present invention is prepared phosgene technique comprises the first constant flow pump, the second constant flow pump, the 3rd constant flow pump, micro mixer, the first micro passage reaction, the second micro passage reaction, product receptor and thermostatic bath; Described second is connected with micro mixer with the 3rd constant flow pump, and described micro mixer is connected with the first micro passage reaction, and described the first micro passage reaction is connected with the second micro passage reaction, and described the second micro passage reaction is connected with product receptor; Described converted in-situ material is carried by the first constant flow pump; The opening for feed of described converted in-situ material is between the first micro passage reaction and the second micro passage reaction; Described micro mixer and first, second micro passage reaction are all placed in thermostatic bath.
Described micro mixer is T-shaped mixing tank; Described first, second micro passage reaction is stainless steel tube; The length of described first, second micro passage reaction is 1.0～20m, and internal diameter is 1.0 mm.Because the mixed effect of material is subject to the restriction of liquid phase material flow velocity, generally can not change the residence time of material in reactor by changing the method for feed velocity.The in the situation that in guaranteeing micro mixer, feed liquid mixed effect being constant, the residence time of length adjustment material that can be by regulating microchannel in micro passage reaction.
The invention has the beneficial effects as follows: compared with prior art, the invention provides a kind of method and device of preparing hypertoxic phosgene based on micro passage reaction technology, the method can meet other organic synthesis field demand to phosgene of laboratory-scale.The method have advantages of extremely short, reaction conversion ratio of reaction conditions gentleness, reaction times and selectivity good; This device has advantages of that simplicity of design, production process are airtight, continuous, have reduced the danger in production, accumulating.
Accompanying drawing explanation
Fig. 1 micro passage reaction is prepared the device schematic flow sheet of phosgene.1-the first constant flow pump wherein, 2-the second constant flow pump, 3-the 3rd constant flow pump, 4-micro mixer, 5-the first micro passage reaction, 6-the second micro passage reaction, 7-product receptor.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
By the anhydrous FeCl of 1g 3be dissolved in 90 mL ethanol, and then add 10 mL CCl 4, be mixed with homogeneous phase solution A.By the H of 30 commercially available wt% 2o 2the concentration dilution of solution is 7.5 wt%, becomes solution B.Converted in-situ material used is commercially available ammoniacal liquor, and concentration dilution is to 1/4 of common concentration, and 6wt%～7wt%, becomes solution C.By intelligent temperature controller, controlling bath temperature is 55 oC, precision ± 0.1 oC.
In experimentation, solution A and B carry by the second and the 3rd constant flow pump respectively, two pumps keeps equal-volume flow, be 5 mL/min, solution A and B carry out enhancing mixed in T-shaped micro mixer, mixed material enters one section of internal diameter 1.0 mm, continues reaction in the micro passage reaction of length 12 m; Solution C is carried by the first constant flow pump, and feed rate is 10 mL/min.
At the second micro passage reaction end, collect product, filtering Fe (OH) 3precipitation, accurately pipette 10 mL filtrates in 50 mL colorimetric cylinders, add sulfuric acid (1+4) acidifying, add PDAB(paradimethy laminobenzaldehyde) solution, make it with absorption product in urea carry out color reaction, colored solutions is diluted to scale marks, with distilled water, makes reference, under 440 nm, measure absorbance.With urea concentration, calculate phosgene output, and calculate phosgene yield.
Experiment records, and phosgene yield is 90%.

Claims (9)

1. the phosgene manufacturing process of a safety, it is characterized in that described technique at least comprises the following steps: by the low-carbon alcohol solution that contains tetracol phenixin, catalyzer and certain density superoxol, by two constant flow pumps, be injected in micro mixer respectively, enter the tetracol phenixin in micro mixer, the low-carbon alcohol solution of catalyzer mixes at micro mixer inner impact with superoxol, then mixing solutions flows in micro passage reaction and carries out catalytic oxidation, generates phosgene; End collecting reaction product at micro passage reaction; Described phosgene preparation technology adopts the method for converted in-situ to consume phosgene; Described phosgene preparation technology adopts the mode of Tritium Immersion Absorption to prevent phosgene leakage; Described micro mixer and micro passage reaction are all placed in thermostatic bath.
2. a kind of safe phosgene manufacturing process according to claim 1, the concentration that it is characterized in that described tetracol phenixin is 5～100 g/L; Described low-carbon alcohol is ethanol.
3. a kind of safe phosgene manufacturing process according to claim 1, is characterized in that described catalyzer is Anhydrous Ferric Chloride; The concentration of described catalyzer is 5～50 g/L.
4. a kind of safe phosgene manufacturing process according to claim 1, is characterized in that the temperature range of thermostatic bath in described reaction process is controlled between 20～80 oC.
5. a kind of safe phosgene manufacturing process according to claim 1, is characterized in that the material that described converted in-situ method adopts is ammoniacal liquor.
6. a kind of safe phosgene manufacturing process according to claim 1, is characterized in that, in described preparation technology, whole reaction unit is immersed in basic solution; Described basic solution is a kind of in weak ammonia or sodium hydroxide solution.
7. a kind of safe phosgene manufacturing process according to claim 1, is characterized in that in described reaction process, and the volumetric flow rate scope of tetracol phenixin, catalyst solution and superoxol is 1.0～20 mL/min.
8. the device of phosgene manufacturing process for safety according to claim 1, is characterized in that described device comprises the first constant flow pump, the second constant flow pump, the 3rd constant flow pump, micro mixer, the first micro passage reaction, the second micro passage reaction, product receptor and thermostatic bath; Described second, third constant flow pump is connected with micro mixer, and described micro mixer is connected with the first micro passage reaction, and described the first micro passage reaction is connected with the second micro passage reaction, and described the second micro passage reaction is connected with product receptor; Described converted in-situ material is carried by the first constant flow pump; The opening for feed of described converted in-situ material is between the first micro passage reaction and the second micro passage reaction; Described micro mixer and first, second micro passage reaction are all placed in thermostatic bath.
9. a kind of safe phosgene preparation facilities according to claim 8, is characterized in that described micro mixer is T-shaped mixing tank; Described first, second micro passage reaction is stainless steel tube; The length of described first, second micro passage reaction is 1.0～20m, and internal diameter is 1.0 mm.
CN201310516134.4A 2013-10-29 2013-10-29 Safe phosgene preparation method and device Pending CN103570018A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107617393A (en) * 2017-09-18 2018-01-23 徐州工程学院 A kind of phosgene reactor for carbon tetrachloride processing equipment
TWI676596B (en) * 2014-06-11 2019-11-11 丹麥商托普索公司 A process for safe production of phosgene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101746736A (en) * 2008-12-10 2010-06-23 中国科学院大连化学物理研究所 Method for preparing hydrogen peroxide by utilizing microchannel technology
CN102092713A (en) * 2010-12-13 2011-06-15 甘肃银光聚银化工有限公司 Method for continuously preparing phosgene
WO2012042130A1 (en) * 2010-09-30 2012-04-05 Aet Group Device and process for continuous phosgenation
CN102603680A (en) * 2012-02-07 2012-07-25 江苏安邦电化有限公司 Method for preparing epoxy chloropropane by cyclizing dichloropropanol in microreactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101746736A (en) * 2008-12-10 2010-06-23 中国科学院大连化学物理研究所 Method for preparing hydrogen peroxide by utilizing microchannel technology
WO2012042130A1 (en) * 2010-09-30 2012-04-05 Aet Group Device and process for continuous phosgenation
CN102092713A (en) * 2010-12-13 2011-06-15 甘肃银光聚银化工有限公司 Method for continuously preparing phosgene
CN102603680A (en) * 2012-02-07 2012-07-25 江苏安邦电化有限公司 Method for preparing epoxy chloropropane by cyclizing dichloropropanol in microreactor

Non-Patent Citations (2)

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Title
L. A. TATAROVA ET AL.: "Reaction of Carbon Tetrachloride with Hydrogen Peroxide", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI676596B (en) * 2014-06-11 2019-11-11 丹麥商托普索公司 A process for safe production of phosgene
US10486972B2 (en) 2014-06-11 2019-11-26 Haldor Topsoe A/S Process for safe production of phosgene
CN107617393A (en) * 2017-09-18 2018-01-23 徐州工程学院 A kind of phosgene reactor for carbon tetrachloride processing equipment

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Application publication date: 20140212