CN101301579A - High-pressure tail gas treatment process in purified terephthalic acid - Google Patents

High-pressure tail gas treatment process in purified terephthalic acid Download PDF

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CN101301579A
CN101301579A CNA2008100393147A CN200810039314A CN101301579A CN 101301579 A CN101301579 A CN 101301579A CN A2008100393147 A CNA2008100393147 A CN A2008100393147A CN 200810039314 A CN200810039314 A CN 200810039314A CN 101301579 A CN101301579 A CN 101301579A
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Prior art keywords
tail gas
mesohigh
oxidation reactor
treatment process
gas treatment
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赵小平
吴利军
张颖
崔德磊
佟飞
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DONGHUA ENVIRONMENT ENGINEERING Co Ltd SHANGHAI
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DONGHUA ENVIRONMENT ENGINEERING Co Ltd SHANGHAI
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Abstract

The present invention discloses a treatment technique for high pressure vent gas of pure terephthalic acid (PTA). PTA vent gas treatment adopts catalytic oxidation technique having noble metal honeycomb catalyst in catalytic oxidation reactor with entrance temperature at 100-650 DEG C and exit temperature at 200-750 DEG C, under pressure of 0.6-2.0 MPa(G); middle-high pressure PTA vent gas enters into catalytic oxidation reactor after being heated by vent gas heat exchanger, harmful and volatile organic substances are transformed into carbon dioxide and water, wherein hydrobromic ether is oxidized to carbon dioxide, water, bromine and hydrogen bromide; vent gas comes out of reactor, enters into an expansion machine after recovering heat and heating feed vent gas in vent gas heat exchanger, enters into an alkaline washing tower after doing work in the expansion machine; the reaction gas is alkaline washed to remove bromine and hydrogen bromide and then discharged from the top of alkaline washing tower. The present invention needs no auxiliary fuel in normal operation course and has advantages of simple technique, low operation cost, no secondary pollution, thorough vent gas treatment and so on.

Description

P-phthalic acid's mesohigh tail gas treatment process
Technical field
The present invention relates to a kind of in industrial production p-phthalic acid (hereinafter to be referred as PTA) process the treatment process of mesohigh tail gas.
Background technology
Has higher pressure from PTA process units high pressure scrubber tail gas discharged, its main component is nitrogen, oxygen and carbon dioxide, contains the harmful components of contaminated environment such as a certain amount of carbon monoxide, methyl acetate, paraxylene, Celfume, methylene bromide and hydrogen bromide simultaneously.Because organic concentration is low in the PTA device exhaust, flow big, have higher pressure, adopts general tail gas treatment process can not satisfy environmental requirement.
The PTA device exhaust generally adopts the directly discharging of the high point of chimney at present, and environment is caused severe contamination.
Also there is part PTA device to adopt high pressure burning (HPCCU) or heat accumulation type thermal oxidation (RTO) technology to come treatment PTA tail gas in addition.High pressure burning process tail gas is used steam heated earlier, is heated to reaction temperature with fuel such as methyl alcohol or propylene again, and process need consume a large amount of fuel, and operating cost is higher, and the burning capacity is bigger; The shortcoming of heat accumulation type thermal oxidation technology is that to add Fuel Consumption big, can not thoroughly remove CO, has part nitrogen in the thermal oxidation process and is oxidized to nitrogen oxide.
Summary of the invention
Technical problem to be solved by this invention is to propose that a kind of technology is simple, SR is little, need not replenish auxiliary fuel, and operating cost is low, the PTA mesohigh tail gas treatment process of non-secondary pollution, thorough tail gas treatment.
In order to achieve the above object, the technical scheme of employing is: a kind of PTA mesohigh tail gas treatment process that the present invention proposes, the heat that utilizes tail gas heat exchanger to reclaim reaction back tail gas are used for the pending tail gas of preheating, and process need not to add fuel.Adopt the noble metal honeycomb catalyst in the catalyst oxidation reactor of the present invention, tail gas is after heating, in pressure 0.6～2.0MPa (G), inlet temperature is 100～650 ℃, outlet temperature is to carry out catalytic oxidation in 200～750 ℃ the catalyst oxidation reactor, harmful volatile organic matter is converted into carbon dioxide and water, bromo-hydrocarbons is oxidized to carbon dioxide, water, bromine and hydrogen bromide.
The inlet temperature of described catalyst oxidation reactor is preferably 300 ℃; Outlet temperature is preferably in below 720 ℃.
As the preferred technical solution of the present invention, tail gas of the present invention preferably enters catalyst oxidation reactor after tail gas heat exchanger is heated to the catalyst initiation temperature.The PTA tail gas heat exchanger is preferably welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger or shell-and-tube heat exchanger.
As catalytic oxidation mechanism of the present invention, following chemical reaction has mainly taken place in the catalyst oxidation reactor:
2CO+O 2＝2CO 2
CH 3COOCH 3+3.5O 2＝3CO 2+3H 2O
C 8H 10+10.5O 2＝8CO 2+5H 2O
CH 3OH+1.5O 2＝CO 2+2H 2O
2CH 3Br+3.5O 2＝2CO 2+3H 2O+Br 2
CH 3Br+1.5O 2＝CO 2+H 2O+HBr
CH 2Br 2+1.5O 2＝CO 2+H 2O+Br 2
CH 2Br 2+O 2＝CO 2+2HBr
As another optimal technical scheme of the present invention, after PTA tail gas carries out catalytic oxidation, preferably enter tail gas heat exchanger recovery section heat.Tail gas through catalytic oxidation treatment behind the recovery section heat, should be sent into the decompressor work done in tail gas heat exchanger.Should send into caustic wash tower then and remove wherein bromine and hydrogen bromide, enter in the atmosphere at last.Is example with sodium hydroxide solution as cleaning solution, and following chemical reaction has mainly taken place in alkaline cleaning procedure:
HBr+NaOH＝NaBr+H 2O
Br 2+2NaOH＝NaBr+NaBrO+H 2O
With respect to prior art, technology of the present invention is simple, reasonable energy utilization, volatile organic matter harmful in the PTA device exhaust is converted into carbon dioxide, water and harmless Bromide, process does not produce oxynitrides, non-secondary pollution, thorough tail gas treatment, testing result satisfy the environment protection control requirements of national Specification fully; In addition, the present invention has very broad opereating specification, in the time of can guaranteeing that content of organics changes in the PTA tail gas, and system's energy stable operation; Have again, the catalyst that the present invention adopts, mechanical strength height, long service life, resistance reduce; At last, the present invention adopts high-efficiency heat pipe heat exchanger or welded plate type heat exchanger or finned tube exchanger or shell-and-tube heat exchanger to reclaim reaction heat to add hot feed tail gas, need not additional fuel in the normal course of operation; Caustic wash tower can thoroughly remove bromine and the hydrogen bromide in the tail gas efficiently.
Description of drawings
Fig. 1 is the processing technological flow figure of PTA mesohigh tail gas of the present invention.
Wherein: 1 is catalyst oxidation reactor; 2 is tail gas heat exchanger; 3 is heater; 4 is decompressor; 5 is caustic wash tower.
The specific embodiment
Below in conjunction with drawings and Examples technology of the present invention is further elaborated.
A kind of PTA mesohigh tail gas treatment process flow process provided by the invention as shown in Figure 1, tail gas derives from certain PTA of company device, design conditions are as shown in table 1.
Certain PTA of company device mesohigh tail gas of table 1 is formed
Figure A20081003931400051
PTA mesohigh tail gas treatment process, comprising that heater 3 goes into operation to heat up preheats, it is characterized in that: after p-phthalic acid's mesohigh tail gas heater via 3 preheats, enter catalyst oxidation reactor 1 and carry out catalytic oxidation, adopt the noble metal honeycomb catalyst in the described catalyst oxidation reactor 1, pressure 0.6～2.0MPa (G), inlet temperature is 100～650 ℃, outlet temperature is 200～750 ℃, harmful volatile organic matter is converted into carbon dioxide and water, bromo-hydrocarbons is oxidized to carbon dioxide, water, bromine and hydrogen bromide, tail gas is sent native system behind the recovery section heat behind the catalytic oxidation in tail gas heat exchanger 2.Charging tail gas enters described catalyst oxidation reactor 1 after tail gas heat exchanger 2 is heated to the catalyst initiation temperature.
Noble metal is the combination of any one or two kinds of noble metals in platinum, the palladium in the noble metal catalyst that adopts in the described catalyst oxidation reactor 1.The inlet temperature of catalyst oxidation reactor 1 is preferably 300 ℃, and outlet temperature is preferred below 720 ℃.
Described tail gas heat exchanger 2 is welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger or shell-and-tube heat exchanger.
Carrying out the go into operation pre-warmed heater 3 that heats up of system is steam heater, electric heater, oil burner or gas burner.
Tail gas after described catalyst oxidation reactor 1 catalytic oxidation treatment, the recovery section heat should be sent into caustic wash tower 5 again and remove wherein bromine and hydrogen bromide after decompressor 4 works done in tail gas heat exchanger 2.
Described caustic wash tower 5 adopts plate column or packed towers, and the alkali lye of employing is any one or two kinds of NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash or saleratus and the aqueous solution of two or more compounds.
Have one to regulate the bypass valve of catalyst oxidation reactor 1 inlet temperature in described catalyst oxidation reactor 1 porch.
Embodiment 1
After the stage part tail gas that goes into operation is heated to 300 ℃ through electric heater 3, enters catalyst oxidation reactor 1 and carry out catalytic oxidation.Gradually with whole tail gas incision catalyst oxidation reactors 1, honeycomb platinum, the palladium metal combination catalyst is fixed on the catalyst fixed bed layer, this moment, catalyst oxidation reactor 1 internal pressure was about 0.9MPa (G), outlet temperature is about 380 ℃, above-mentioned tail gas carries out catalytic oxidation in catalyst oxidation reactor 1, harmful volatile organic matter is converted into carbon dioxide and water, bromo-hydrocarbons is oxidized to carbon dioxide, water and bromine, and discharge a large amount of heat, tail gas after the catalytic reaction is sent into decompressor 4 after tail gas heat exchanger 2 reclaims heat, tail gas behind the expansion working is sent into sodium hydroxide solution caustic wash tower 5, and the tail gas after the alkali cleaning directly is discharged in the atmosphere.Detect sending into the laboratory after the discharging gas sampling after handling, after testing, the volatile organic content that dimethylbenzene and NMHC etc. are harmful in the cleaning of off-gas is as shown in table 2.
Certain economizes environmental monitoring central station Monitoring Data and control index table 2
The pollutant title Concentration of emission (mg/m 3) Concentration of emission evaluation criterion (mg/m 3)
Dimethylbenzene 25 70
NMHC 96 120
Annotate: concentration of emission is repeatedly the mean value of sampling.
Embodiment 2
Catalyst oxidation reactor 1 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 1 internal pressure is about 0.7MPa (G), inlet temperature and is about 150 ℃, outlet temperature and is about 220 ℃, and caustic wash tower 5 used alkali lye are potassium hydroxide solution, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 31,98mg/m 3, reach national discharge standard of air pollutants.
Embodiment 3
Catalyst oxidation reactor 1 adopts the honeycomb palladium metal catalyst, and catalyst oxidation reactor 1 internal pressure is about 0.8MPa (G), inlet temperature and is about 250 ℃, outlet temperature and is about 310 ℃, and caustic wash tower 5 used alkali lye are sodium carbonate liquor, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 28,97mg/m 3, reach national discharge standard of air pollutants.
Embodiment 4
Catalyst oxidation reactor adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 1 internal pressure is about 1.0kPa (G), inlet temperature and is about 320 ℃, outlet temperature and is about 400 ℃, and caustic wash tower 5 used alkali lye are sodium bicarbonate solution, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 27,95mg/m 3, reach national discharge standard of air pollutants.
Embodiment 5
Catalyst oxidation reactor adopts the honeycomb palladium metal catalyst, and catalyst oxidation reactor 1 internal pressure is about 1.1MPa (G), inlet temperature and is about 380 ℃, outlet temperature and is about 450 ℃, and caustic wash tower 5 used alkali lye are solution of potassium carbonate, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 26,94mg/m 3, reach national discharge standard of air pollutants.
Embodiment 6
Catalyst oxidation reactor 1 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 1 internal pressure is about 1.2MPa (G) inlet temperature and is about 420 ℃, outlet temperature and is about 480 ℃, and caustic wash tower 5 used alkali lye are potassium bicarbonate solution, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 25,93mg/m 3, reach national discharge standard of air pollutants.
Embodiment 7
Catalyst oxidation reactor 1 adopts the honeycomb palladium metal catalyst, catalyst oxidation reactor 1 internal pressure is about 1.4MPa (G), inlet temperature and is about 480 ℃, outlet temperature and is about 550 ℃, caustic wash tower 5 used alkali lye are the mixed solution of NaOH and sodium carbonate, and all the other are with embodiment 1.After testing, in the clean cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 24,92mg/m 3, reach national discharge standard of air pollutants.
Embodiment 8
Catalyst oxidation reactor 1 adopts the honeycomb platinum metal catalyst, catalyst oxidation reactor 1 internal pressure is about 1.6MPa (G) inlet temperature and is about 540 ℃, outlet temperature and is about 600 ℃, caustic wash tower 5 used alkali lye are the mixed solution of NaOH and sodium acid carbonate, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 22,92mg/m 3, reach national discharge standard of air pollutants.
Embodiment 9
Catalyst oxidation reactor 1 adopts the honeycomb palladium metal catalyst, catalyst oxidation reactor 1 internal pressure is about 1.7MPa (G), inlet temperature and is about 590 ℃, outlet temperature and is about 660 ℃, caustic wash tower 5 used alkali lye are the mixed solution of NaOH, sodium carbonate and sodium acid carbonate, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 20,89mg/m 3, reach national discharge standard of air pollutants.
Embodiment 10
Catalyst oxidation reactor 1 adopts the honeycomb platinum metal catalyst, catalyst oxidation reactor 1 internal pressure is about 1.8MPa (G), inlet temperature and is about 650 ℃, catalyst oxidation reactor outlet temperature and is about 730 ℃, caustic wash tower 5 used alkali lye are the mixed solution of NaOH, potassium hydroxide, sodium carbonate and sodium acid carbonate, and all the other are with embodiment 1.After testing, in the cleaning of off-gas concentration of dimethylbenzene and NMHC be respectively 18,85mg/m 3, reach national discharge standard of air pollutants.
The PTA mesohigh exhaust gas processing device that Zai Now field test monitoring is put certain company is constructed and put into operation back on probation, be subjected to the trust of China Environmental Monitoring General Station, certain economizes the requirement of environmental monitoring central station according to China Environmental Monitoring General Station, the PTA emission-control equipment has been carried out the spot sampling monitoring checked and accepted, testing result satisfies the environment protection control requirements of national Specification fully.

Claims (9)

1, p-phthalic acid's mesohigh tail gas treatment process, comprising that heater (3) goes into operation preheats, it is characterized in that: after p-phthalic acid's mesohigh tail gas heater via (3) preheats, enter catalyst oxidation reactor (1) and carry out catalytic oxidation, adopt the noble metal honeycomb catalyst in the described catalyst oxidation reactor (1), pressure 0.6～2.0MPa (G), inlet temperature is 100～650 ℃, outlet temperature is 200～750 ℃, harmful volatile organic matter is converted into carbon dioxide and water, bromo-hydrocarbons is oxidized to carbon dioxide, water, bromine and hydrogen bromide, tail gas is sent native system behind the recovery section heat behind the catalytic oxidation in tail gas heat exchanger (2).
2, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: catalyst oxidation reactor (1) inlet temperature is preferably 300 ℃, and outlet temperature is preferred below 720 ℃.
3, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: charging tail gas is heated to the catalyst initiation temperature through tail gas heat exchanger (2) and enters described catalyst oxidation reactor (1).
4, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: the noble metal in the described noble metal honeycomb catalyst is the combination of any one or two kinds of noble metals in platinum, the palladium.
5, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: described tail gas heat exchanger (2) is welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger or shell-and-tube heat exchanger.
6, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: carrying out the go into operation pre-warmed heater (3) that heats up of system is steam heater or electric heater or oil burner or gas burner.
7, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: the tail gas after described catalyst oxidation reactor (1) catalytic oxidation treatment, the recovery section heat is sent into caustic wash tower (5) more again and is removed wherein bromine and hydrogen bromide after decompressor (4) work done in tail gas heat exchanger (2).
8, according to the described p-phthalic acid's mesohigh of claim 7 tail gas treatment process, it is characterized in that: described caustic wash tower (5) adopts plate column or packed tower, and the alkali lye of employing is any one or two kinds of NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash or saleratus and the aqueous solution of two or more compounds.
9, according to the described p-phthalic acid's mesohigh of claim 1 tail gas treatment process, it is characterized in that: have one to regulate the bypass valve of catalyst oxidation reactor (1) inlet temperature in described catalyst oxidation reactor (1) porch.
CNA2008100393147A 2008-06-20 2008-06-20 High-pressure tail gas treatment process in purified terephthalic acid Pending CN101301579A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940869A (en) * 2010-06-13 2011-01-12 浙江逸盛石化有限公司 Purification method and device of exhaust gas of purified terephthalic acid oxidizing device
CN102824813A (en) * 2011-06-14 2012-12-19 逸盛大化石化有限公司 Processing technology of oxidation exhaust of PTA apparatus
CN102908884A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Method for purifying waste gas from production of purified terephthalic acid
CN108057330A (en) * 2017-12-22 2018-05-22 宁夏公路勘察设计院有限责任公司 A kind of PTA oxidized tail gas purification and bromine retracting device and technique

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940869A (en) * 2010-06-13 2011-01-12 浙江逸盛石化有限公司 Purification method and device of exhaust gas of purified terephthalic acid oxidizing device
CN101940869B (en) * 2010-06-13 2013-08-07 浙江逸盛石化有限公司 Purification method and device of exhaust gas of purified terephthalic acid oxidizing device
CN102824813A (en) * 2011-06-14 2012-12-19 逸盛大化石化有限公司 Processing technology of oxidation exhaust of PTA apparatus
CN102908884A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Method for purifying waste gas from production of purified terephthalic acid
CN102908884B (en) * 2011-08-01 2015-04-15 中国石油化工股份有限公司 Method for purifying waste gas from production of purified terephthalic acid
CN108057330A (en) * 2017-12-22 2018-05-22 宁夏公路勘察设计院有限责任公司 A kind of PTA oxidized tail gas purification and bromine retracting device and technique

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Open date: 20081112