CN104492237A - Recovery method of phosgene synthesis tail gas - Google Patents
Recovery method of phosgene synthesis tail gas Download PDFInfo
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- CN104492237A CN104492237A CN201410825649.7A CN201410825649A CN104492237A CN 104492237 A CN104492237 A CN 104492237A CN 201410825649 A CN201410825649 A CN 201410825649A CN 104492237 A CN104492237 A CN 104492237A
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- phosgene
- tail gas
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- warm water
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a recovery method of phosgene synthesis tail gas. The recovery method is characterized in that a great amount of excessive phosgene synthesis tail gas in the phosgene production process can directly react with chlorine without being pressurized to generate phosgene, so that the recycling of CO is realized, and the utilization rate of the CO is increased. The recovery method comprises the following steps: a. leading out the phosgene synthesis unit tail gas from an outlet of a phosgene storage tank; b. heating the led-out synthesis tail gas to 30 DEG C by virtue of a pipeline which is wound with an electric heating band, and enabling the tail gas to enter a mixer after the tail gas is converged; c. conveying the chlorine to the mixer through a raw material gas pipeline to obtain mixed gas; and D. sending the mixed gas to a reactor to be subjected to the phosgene synthesis reaction. By adopting the method, raw material gas in the tail gas can be adequately utilized, the emission of the phosgene synthesis tail gas is reduced, the utilization rate of the raw material is increased, and the environmental pollution is reduced.
Description
Technical field
The present invention relates to a kind of method extracting raw material in chemically industrial tail gas, especially from a kind of recovery method of tail gas of optical self-encoding process generation, in order to solve the exploitation problem of optical self-encoding tail gas.
Background technology
Optical self-encoding operation is the important supporting operation that TDI produces, in optical self-encoding process, have large quantity of exhaust gas generate, wherein containing a large amount of CO, micro-phosgene, toluene and inert gas etc., under existing technique, these waste gas are all sent to tail gas and are destroyed system, wherein CO reaches more than 60%, these CO do not reacted with alkali lye are directly discharged in air, not only can cause environmental pollution, and have impact on economic benefit and the competitiveness of enterprise.The present invention utilizes the tail gas recycle produced in phosgene production process and has done further investigation, by analysis, detects, finds that wherein CO content is more than 60%, is badly in need of a kind of new method of research for this reason and reclaims optical self-encoding tail gas.
Summary of the invention
The object of the invention is for solving the problem and providing a kind of recovery method of optical self-encoding tail gas.
For achieving the above object, the technical scheme that the present invention takes is: a kind of recovery method of optical self-encoding tail gas, it is characterized in that: the tail gas being main component with CO photoreactive gas in phosgene production is incorporated into independent reaction system, again produce phosgene with chlorine reaction, concrete steps are as follows:
A, by optical self-encoding unit tail gas from phosgene reaction system reservoir (11) outlet draw, gas mixer (1) is entered by after the pipeline heating to 30 DEG C that is tied with heat tape, meanwhile, chlorine is delivered to gas mixer (1) by unstripped gas pipeline and mixes, CO:CL by volume
2=1.1:1;
Send into phosgene reactor (2) after b, mixing and carry out optical self-encoding reaction, reaction pressure controls as 0.3-0.35MPa;
The reacted reactant of c, optical self-encoding enters guard reactor (4);
D, from guard reactor (4) phosgene out through subcooler B(6) after cooling, then be condensed into cold light gas by condenser (7);
E, condenser 7 have current divider function, enter in phosgene storage tank (8) by crossing cold light gas, and fixed gas enters tail gas absorber (9) and carries out absorption process;
Described independent reaction system is: phosgene reaction system reservoir (11) outlet access gas mixer (1); unstripped gas chlorine pipeline also accesses gas mixer (1); gas mixer (1) outlet connects phosgene reactor (2); phosgene reactor (2) outlet connects guard reactor (4); guard reactor (4) outlet connects cooler B(6); cooler B(6) outlet connection condenser (7); condenser (7) outlet connects phosgene storage tank (8), and phosgene storage tank (8) outlet connects tail gas absorber (9).
Described independent reaction system support is provided with Water heating system, Water heating system is used for shifting out reaction heat and avoiding phosgene condensation in reactor, described Warm water circulation system is: warm water enters warm water pump (3) from warm water tank (10), again by or walk around cooler A(5) enter the housing of phosgene reactor (2), then turn back to warm water pump (3), temperature is by regulating warm water flow to control; Tributary supply guard reactor (4) chuck warm water of warm water pump (3), if the chlorine having unreacted complete enters guard reactor (4), the temperature difference TD produced by guard reactor (4) judges; Cooler A(5) medium be water;
To the pipeline of guard reactor (4), in-line analyzer is installed at phosgene reactor (2), detects free chlorine contents continuously, guarantee Cl
2react completely.
Leak to detect phosgene, the minimum reflux pipeline of warm water pump (3) to phosgene storage tank (8) is equipped with analyzer, continuously the pH value of monitoring warm water.
Cooler B(6) medium be water, the medium of condenser (7) is freezing toluene.
The invention has the beneficial effects as follows: the newly-built a set of independently phosgene reaction system of the present invention, different at 6 MPa reaction conditions from original pressure, but under 0.3-0.35MPa condition, by optical self-encoding tail gas directly and chlorine is mixed carries out reaction generation phosgene, no longer compression boosting is carried out to tail gas, most economical achieving makes full use of the CO in tail gas, decrease the discharge of optical self-encoding tail gas, optical self-encoding tail gas capacity declines more than 95%, improve raw material availability, decrease the pollution to environment.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention.
In figure: 1-gas mixer; 2-phosgene reactor; 3-warm water pump; 4-guard reactor; 5-cooler A; 6-cooler B; 7-condenser; 8-phosgene storage tank; 9-tail gas absorber; 10-warm water tank, 11-phosgene reaction system reservoir.
Detailed description of the invention
Embodiment 1:
See Fig. 1, the phosgene reaction system reservoir outlet pressure position 0.35MPa of process units, temperature-12 DEG C, analyzes exit gas composition, and it is mainly composed as follows:
1# line: CO 69 .1384%, HCl 0.024%, COCl2 30.82%, C2H5Cl 0.0148%;
2# line: CO 69.157%, HCl 0.02%, COCl2 30.82%, C2H5Cl 0.003%;
Main equipment specification:
Gas mixer φ 200 × 3000,
Phosgene reactor φ 1700 × 2500/ φ 1400 × 2500,
Warm water pump 210m3/hr 20m 22kw 1450r/min,
Guard reactor φ 1000/1100 × 1244,
Cooler A φ 700 × 3000 73.5m2/63.7m2,
Cooler B φ 500 × 3500 34.4m2,
Condenser φ 400 × 3000 21.5m2,
Phosgene storage tank Φ 800 × 4543,
Tail gas absorber φ 250/400 × 4543/ φ 200 × 3700
The tail gas being main component with CO photoreactive gas in phosgene production is incorporated into independent reaction system, and again produce phosgene with chlorine reaction, concrete steps are as follows:
A, optical self-encoding unit tail gas is exported extraction from phosgene reaction system reservoir 11, gas mixer 1 is entered by after the pipeline heating to 30 DEG C that is tied with heat tape, meanwhile, chlorine is delivered to gas mixer 1 by unstripped gas pipeline and mixes, CO:CL by volume
2=1.1:1;
Send into phosgene reactor 2 after b, mixing and carry out optical self-encoding reaction, reaction pressure controls as 0.3-0.35MPa;
The reacted reactant of c, optical self-encoding enters guard reactor 4;
D, from guard reactor (4) phosgene out after subcooler B 6 cools, then be condensed into cold light gas by condenser 7;
E, condenser 7 have current divider function, enter in phosgene storage tank 8 by crossing cold light gas, and fixed gas enters tail gas absorber 9 and carries out absorption process;
Described independent reaction system is: phosgene reaction system reservoir 11 exports access gas mixer 1; unstripped gas chlorine pipeline also accesses gas mixer 1; gas mixer 1 exports and connects phosgene reactor 2; phosgene reactor 2 exports and connects guard reactor 4; guard reactor 4 exports and connects cooler B 6; cooler B 6 exports and connects condenser 7, and condenser 7 exports and connects phosgene storage tank 8, and phosgene storage tank 8 exports and connects tail gas absorber 9.
Described independent reaction system support is provided with Water heating system, Water heating system is used for shifting out reaction heat and avoiding phosgene condensation in reactor, described Warm water circulation system is: warm water enters warm water pump 3 from warm water tank 10, pass through again or walk around the housing that cooler A 5 enters phosgene reactor 2, then turn back to warm water pump 3, temperature is by regulating warm water flow to control; A tributary supply guard reactor 4 chuck warm water of warm water pump 3, if the chlorine having unreacted complete enters guard reactor 4, the temperature difference TD produced by guard reactor 4 judges; The medium of cooler A 5 is water;
In-line analyzer installed by the pipeline of phosgene reactor 2 to guard reactor 4, detects free chlorine contents continuously, guarantee Cl
2react completely.
Leak to detect phosgene, the minimum reflux pipeline of warm water pump 3 to phosgene storage tank 8 is equipped with analyzer, continuously the pH value of monitoring warm water.
The medium of cooler B 6 is water, and the medium of condenser 7 is freezing toluene.
As newly-built optical self-encoding cellular system fluctuation or fault, the phosgene reaction system reservoir 11 of then closing process units is exported to the magnetic valve A of blender 1, the phosgene reaction system reservoir opening process units is exported to the magnetic valve B on process units phosgene tail gas absorption tower, ensures that original production normally runs.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a recovery method for optical self-encoding tail gas, is characterized in that: the tail gas being main component with CO photoreactive gas in phosgene production is incorporated into independent reaction system, and again produce phosgene with chlorine reaction, concrete steps are as follows:
A, by optical self-encoding unit tail gas from phosgene reaction system reservoir (11) outlet draw, gas mixer (1) is entered by after the pipeline heating to 30 DEG C that is tied with heat tape, meanwhile, chlorine is delivered to gas mixer (1) by unstripped gas pipeline and mixes, CO:CL by volume
2=1.1:1;
Send into phosgene reactor (2) after b, mixing and carry out optical self-encoding reaction, reaction pressure controls as 0.3-0.35MPa;
The reacted reactant of c, optical self-encoding enters guard reactor (4);
D, from guard reactor (4) phosgene out through subcooler B(6) after cooling, then be condensed into cold light gas by condenser (7);
E, enter in phosgene storage tank (8) by crossing cold light gas, fixed gas enters tail gas absorber (9) to carry out absorptions and processes;
Described independent reaction system is: phosgene reaction system reservoir (11) outlet access gas mixer (1); unstripped gas chlorine pipeline also accesses gas mixer (1); gas mixer (1) outlet connects phosgene reactor (2); phosgene reactor (2) outlet connects guard reactor (4); guard reactor (4) outlet connects cooler B(6); cooler B(6) outlet connection condenser (7); condenser (7) outlet connects phosgene storage tank (8), and phosgene storage tank (8) outlet connects tail gas absorber (9).
2. the recovery method of a kind of optical self-encoding tail gas as claimed in claim 1, it is characterized in that described independent reaction system support is provided with Water heating system: warm water enters warm water pump (3) from warm water tank (10), again by or walk around cooler A(5) enter the housing of phosgene reactor (2), then turn back to warm water pump (3), temperature is by regulating warm water flow to control; Tributary supply guard reactor (4) chuck warm water of warm water pump (3); Cooler A(5) medium be water.
3. the recovery method of a kind of optical self-encoding tail gas as claimed in claim 1, is characterized in that: to the pipeline of guard reactor (4), install in-line analyzer at phosgene reactor (2).
4. the recovery method of a kind of optical self-encoding tail gas as claimed in claim 2, is characterized in that: on the minimum reflux pipeline of warm water pump (3) to phosgene storage tank (8), analyzer is housed, continuously the pH value of monitoring warm water.
5. the recovery method of a kind of optical self-encoding tail gas as claimed in claim 1, is characterized in that: cooler B(6) medium be water, the medium of condenser (7) is freezing toluene.
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| CN201410825649.7A CN104492237A (en) | 2014-12-28 | 2014-12-28 | Recovery method of phosgene synthesis tail gas |
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| CN201410825649.7A CN104492237A (en) | 2014-12-28 | 2014-12-28 | Recovery method of phosgene synthesis tail gas |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827111A (en) * | 2017-11-21 | 2018-03-23 | 万华化学集团股份有限公司 | A kind of optical self-encoding method of adjustable spraying apparatus and circulation of tail gas reuse |
| CN109678194A (en) * | 2019-01-09 | 2019-04-26 | 中国原子能科学研究院 | A kind of ceria chloridizing unit |
| CN111111432A (en) * | 2019-12-31 | 2020-05-08 | 南京工大环境科技有限公司 | Method for treating tail gas of phosgenation reaction |
| CN114146652A (en) * | 2021-12-06 | 2022-03-08 | 甘肃银光聚银化工有限公司 | Phosgene synthesis reaction waste gas recycling method |
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| US20070276158A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Material Science Ag | Processes for separating carbon monoxide from a hydrogen chloride-containing gas |
| CN101445238A (en) * | 2007-11-29 | 2009-06-03 | 拜尔材料科学股份公司 | Phosgene production process for reducing CO emission |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070276158A1 (en) * | 2006-05-23 | 2007-11-29 | Bayer Material Science Ag | Processes for separating carbon monoxide from a hydrogen chloride-containing gas |
| CN101448739A (en) * | 2006-05-23 | 2009-06-03 | 拜尔材料科学股份公司 | Method for separating carbon monoxide from hydrogen chloride-containing gas |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827111A (en) * | 2017-11-21 | 2018-03-23 | 万华化学集团股份有限公司 | A kind of optical self-encoding method of adjustable spraying apparatus and circulation of tail gas reuse |
| CN107827111B (en) * | 2017-11-21 | 2022-07-12 | 万华化学(福建)有限公司 | Adjustable ejector and phosgene synthesis method for recycling tail gas |
| CN109678194A (en) * | 2019-01-09 | 2019-04-26 | 中国原子能科学研究院 | A kind of ceria chloridizing unit |
| CN109678194B (en) * | 2019-01-09 | 2024-02-23 | 中国原子能科学研究院 | Cerium dioxide chlorination device |
| CN111111432A (en) * | 2019-12-31 | 2020-05-08 | 南京工大环境科技有限公司 | Method for treating tail gas of phosgenation reaction |
| CN111111432B (en) * | 2019-12-31 | 2022-05-27 | 南京工大环境科技有限公司 | Method for treating tail gas of phosgenation reaction |
| CN114146652A (en) * | 2021-12-06 | 2022-03-08 | 甘肃银光聚银化工有限公司 | Phosgene synthesis reaction waste gas recycling method |
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Application publication date: 20150408 |