CN102908884B - Method for purifying waste gas from production of purified terephthalic acid - Google Patents
Method for purifying waste gas from production of purified terephthalic acid Download PDFInfo
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- CN102908884B CN102908884B CN201110217408.0A CN201110217408A CN102908884B CN 102908884 B CN102908884 B CN 102908884B CN 201110217408 A CN201110217408 A CN 201110217408A CN 102908884 B CN102908884 B CN 102908884B
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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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention discloses a method for purifying waste gas from the production of a purified terephthalic acid. The method comprises: heating oxidation off-gas from the production process of the purified terephthalic acid for temperature rise via a heat exchanger and a preheater; then feeding into a catalytic combustion reactor; after the heat exchange between the exit off-gas of the catalytic combustion reactor and the entrance waste gas of the catalytic combustion reactor, feeding the exit off-gas into an alkaline tower; feeding off-gas from the alkaline tower into an adsorption column for an adsorption drying treatment; and respectively performing reuse or energy recovery to effluent gas after the drying treatment. According to the process adopted by the method of the present invention, only a few changes needed to be made to an existing purified terephthalic acid production apparatus, and production by the apparatus is not affected, so the method is particularly suitable for the transformation of the existing purified terephthalic acid production apparatus for an environmental protection purpose.
Description
Technical field
The present invention relates to a kind of purification method of waste gas, belong to waste gas purification field.This waste gas is from the oxidized tail gas discharged in existing PTA Equipment production process, and its key component comprises benzene, dimethylbenzene, acetic acid, methyl acetate, Bromofume, carbon monoxide etc.
Background technology
P-phthalic acid (PTA) is a kind of important industrial chemicals.In the production process of p-phthalic acid, containing components such as benzene, dimethylbenzene, acetic acid, methyl acetate, Bromofume, carbon monoxide in the oxidation gaseous effluent of generation.Most of pure terephthalic acid producing devices of China's construction before 2000, its oxidation gaseous effluent produced mostly not through effectively processing and discharging directly into atmosphere, causes very large pollution to atmospheric environment.
CN96195949.5 discloses a kind of p-phthalic acid's tail gas that contains at interior waste gas processing method.It comprises makes waste gas under high pressure carry out catalytic combustion, and the gas processed is sent into energy-recuperation system, it is characterized by: containing the compound that can be transformed into gaseous bromine compound when original bromide or catalytic combustion in waste gas streams, or in the liquid phase to the compound of the manufactured materials of the energy-recuperation system effect of being corrosive; Containing the waste gas of above-mentioned original bromide through catalytic combustion; The gas of the gaseous bromine compound containing follow-up generation after treatment enters energy-recuperation system; Controlled pressure and temperature conditions, to prevent above-mentioned various bromide by there is condensation during energy-recuperation system, and by after energy-recuperation system, above-mentioned follow-up bromide is removed from the gas processed.This method is a kind of HIGH PRESSURE TREATMENT technology, processed before tail gas enters decompressor, comparatively tight with the combination of process units, be relatively applicable to newly-built PTA Equipment, waste gas catalytic combustion treating apparatus and process units design simultaneously, build simultaneously, come into operation simultaneously.But for existing PTA Equipment, if the process of its tail gas directly adopts this technology, the gas after catalytic combustion process goes the off-gas expander of process units to recover energy, and is difficult to the air inlet requirement meeting off-gas expander; And off-gas expander is directly closely connected with process units, and expensive, if the off-gas expander more renewed, the huge waste of resource certainly will be caused, turn improve vent gas treatment expense simultaneously.Therefore, concerning existing PTA Equipment, the technology described in CN96195949.5 is also not suitable for.
JP-A-559517 discloses a kind of high-pressure catalytic burn processing method processing p-phthalic acid's tail gas, and after mainly utilizing catalytic combustion technology to process tail gas, after process, gas discharges after energy regenerating.Except it does not consider HBr, Br
2process outside, described in its handling process and patent CN96195949.5, flow process is basically identical.This technology is not suitable for the vent gas treatment of existing process units equally.
The domestic pure terephthalic acid producing device built in the past in 2000, its oxidized tail gas is mostly through effectively processing and discharging directly into atmosphere.Oxidized tail gas mainly contains three whereabouts: see Fig. 3.Under normal production conditions, except small part waste gas was directly discharged by aiutage before adsorption tower, all the other waste gas carry out adsorption treatment through adsorption tower.Waste gas after adsorption tower process some for device highpressure pneumatic system, all the other waste gas recover energy through off-gas expander.Waste gas after off-gas expander has 3 whereabouts: a part is used for pressing blast system in device; A part is used for the regeneration of adsorption tower, and the regeneration off gases of generation is discharged by aiutage; All the other most of waste gas are discharged by aiutage.In fact, this main purpose using single adsorption technology as process means, be only used to obtain the blast system of dry inert gas for device, all be discharged in air by the organic component adsorbed in the regenerative process of adsorption tower in adsorption process, huge pollution is caused to air, meanwhile, adsorption process for the carbon monoxide in waste gas without any treatment effect.
To this organic exhaust gas containing benzene, dimethylbenzene, acetic acid, methyl acetate, Bromofume, carbon monoxide etc., catalytic combustion is a kind of suitable processing method beyond doubt, and it has, and operating temperature is low, unit scale is little, the advantage of non-secondary pollution.But the processing method that CN96195949.5 and JP-A-559517 introduces, all needs to replace adsorption tower, sets up the oxidized tail gas of high-pressure catalytic burning processing device for the treatment of high pressure.These two kinds of technology are for newly-built PTA Equipment, applicable, but for not taking the existing PTA Equipment of effective waste gas pollution control and treatment measure, due to the inlet air conditions of the harshness of the waste gas demand fulfillment off-gas expander after catalytic combustion, therefore, not only in technology and engineering, there is difficulty, and have influence on the normal production of PTA Equipment; If supporting off-gas expander again, then the cost for the treatment of apparatus is made greatly to increase.
Therefore, concerning existing terephthalic acid production plant, the Treatment process that its vent gas treatment adopts, first the existing need of production of device should be met, namely treated purified gas will meet the air inlet requirement of off-gas expander, do not affect the production of device, also will meet the discharge standard of country simultaneously, this just needs to select the treatment technology that is applicable to and device according to the present situation of phthalic acid process units.
Summary of the invention
The present invention has taken into full account the present situation of existing pure terephthalic acid producing device, effectively make use of the exhaust treatment system of existing apparatus, for the feature of p-phthalic acid's oxidized tail gas, under the condition not affecting process units running, propose the processing method of waste gas.
The purification method of p-phthalic acid's process gas of the present invention comprises following content: the oxidized tail gas of p-phthalic acid's production process heats up through heat exchanger and preheater, then catalytic combustion reactor is entered, caustic wash tower is entered after catalytic combustion reactor outlet tail gas and inlet exhaust gases heat exchange, the tail gas of caustic wash tower discharge enters adsorption tower and carries out adsorption dry process, and the discharge gas after dry process carries out reuse respectively, carries out energy regenerating.
In the inventive method, the oxidized tail gas of p-phthalic acid's production process first through entrainment trap, and then can carry out catalytic combustion process.
In the inventive method, catalyticing combustion process can adopt catalytic combustion method of the prior art, is filled with honeycomb catalyst combustion catalyst in catalytic combustion reactor, it supports precious metals pt, Pd and CeO
2isoreactivity component.The entrance bed temperature scope of catalytic combustion reactor is generally 250 ~ 400 DEG C, and use space velocity range is 10000 ~ 50000h
-1.
In the inventive method, adsorption tower and energy-recuperation system adopt the existing apparatus in p-phthalic acid's production system, do not need to change.Newly-built part comprises catalytic combustion system and caustic washing system.Catalytic combustion system identical with the pressure of p-phthalic acid's production process oxidized tail gas with caustic washing system pressure (disregarding pressure loss during flowing), is generally 0.7 ~ 1.2MPa.
Adsorption dry facility is connected with catalytic combustion-alkali cleaning facility and is used, catalytic combustion-alkali cleaning facility is provided with bypass, when newly constructed facility (catalytic combustion-caustic washing system) fault, bypass valve can be opened automatically, tail gas carries out adsorption dry process by original adsorption dry facility, guarantee the normal operation of process units blast system and off-gas expander, avoid the disastershutdown of process units.The automatic start signal of bypass valve from the fault-signal of catalytic combustion-alkali cleaning facility, the such as high limited signal of temperature of catalytic combustion reactor outlet, the fault-signal etc. of alkali cleaning circulating pump.
In the inventive method, the wind that the discharge gas after energy regenerating is further used for device send power.
In processing method of the present invention, the discharging waste gas of existing PTA Equipment can be made to meet national standard, and take full advantage of the adsorption system of existing apparatus, on process units without any impact, any transformation is not needed to energy-recuperation system, special under the condition of newly-built partial fault, also can not affect the blast system of process units and the running of off-gas expander.Carry out construction under the condition that newly constructed facility can run well at process units, can not process units be affected.Flow process of the present invention is simple, stable operation, and purifying rate is high, non-secondary pollution, investment cost is low, and waste heat can also utilize, also recover energy by off-gas expander, by adsorption dry generation device conveying wind, there is good economic benefit, social benefit and environmental benefit.The inventive method is changed very little to existing PTA Equipment, can make full use of all devices of existing p-phthalic acid, invest lower, be suitable for the oxidized tail gas process of existing pure terephthalic acid producing device.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Wherein: 1-oxidized tail gas (high pressure), 2-heat exchanger, 3-heater, 4-catalytic combustion reactor, 5-caustic wash tower, 6-alkali liquor storage tank, 7-circulating pump, 8-transfer valve group, the original adsorption system of 9-, 10-purified gas (discharge or reuse).
Fig. 2 is existing apparatus vent gas treatment schematic flow sheet.
Wherein: 1-oxidized tail gas (high pressure), 102-treating apparatus on-position of the present invention, 103-adsorption tower, 104-off-gas expander, 105-aiutage, the in line waste gas of 106-, 107-regeneration off gases, discharging waste gas after 108-decompressor, the import of 109-regeneration gas, 110-high-pressure blast send and nitrogen system, presses wind to send in 111-.
Fig. 3 is existing apparatus vent gas treatment FB(flow block).
Detailed description of the invention
In the purification method of p-phthalic acid's process gas of the present invention, the oxidized tail gas of p-phthalic acid's production process enters treating apparatus after entrainment trap, heat up after heat exchanger and preheater, waste gas after intensification enters catalytic combustion reactor, is oxidized to carbon dioxide, water, HBr and Br
2, waste gas enters caustic wash tower subsequently, HBr and Br in waste gas
2by alkali liquor absorption, the purified gas major part obtained goes the original adsorption system of device to carry out adsorption dry process, and purified gas after an adsorption dry part is for the production of the blast system of device, and remaining waste gas to recover energy discharge through off-gas expander.
Exhaust-gas treatment flow process of the present invention is shown in Fig. 1.
The pressure of oxidized tail gas pressure after entrainment trap of existing pure terephthalic acid producing device is 0.9MPa, temperature about 200 DEG C.First waste gas heat up through heat exchanger and heater by the present invention, and make it reach the reaction temperature of catalytic combustion, then enter catalytic combustion reactor, under the effect of catalyst, in waste gas, organic component and carbon monoxide are oxidized to carbon dioxide, water, HBr and Br
2.
Except containing CO in gas after catalytic combustion process
2and H
2outside O, also containing HBr, Br
2, also need to carry out alkali cleaning process, to remove HBr and Br contained in gas
2.Filler is equipped with in caustic wash tower inside, and it provides mass transfer surfaces for solution-air in tower two contacts, and this filler has larger specific area and good wetability, also has compared with high voidage, the advantage such as gas-flow resistance is little, corrosion-resistant, mechanical strength is large.Demist silk screen and filler are arranged at caustic wash tower top, to remove most of moisture.Cleaning solution recycles, and liquid storage section and circulating water chennel UNICOM are arranged at caustic wash tower bottom.Along with the consumption of alkali lye, the basicity of cleaning solution reduces gradually.Spent lye goes plant area's sewage farm process.The absorbing liquid of caustic wash tower is mainly containing two or more in the components such as NaOH, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium sulfite.
Main containing N in purified gas after alkali cleaning
2, CO
2and H
2o, pollution components is thoroughly removed, and now purified gas directly discharges and meets discharging standards.But also containing a large amount of water vapour in purified gas now, be not suitable for the mass transport wind being directly used in device, also need the mass transport that could be used for device after adsorption dry removes water vapour, the air inlet requirement of off-gas expander could be met.Present invention utilizes the waste gas adsorption treatment facility that process units is original, adsorption dry process is carried out to purified gas.The adsorbent that adsorption dry facility adopts is active carbon and silica gel, mainly carries out drying process to purified gas.A gas part after adsorption dry process is for the production of the blast system of device, and remaining waste gas discharges air after off-gas expander recovers energy.
Below in conjunction with example, the specific embodiment of the present invention is described.
Certain existing PTA Equipment, its original vent gas treatment flow process is shown in Fig. 2, and the discharge capacity of its oxidized tail gas is 75000Nm
3/ h, waste gas total hydrocarbon concentration 3000 mg/m
3, benzene 150mg/m
3, Bromofume 70mg/m
3, carbonomonoxide concentration 5000 μ L/L.
The vent gas treatment flow process proposed according to the present invention as shown in Figure 1.Waste gas enters heat exchanger (heating) and heater after entrainment trap, and waste gas enters catalytic combustion reactor after being preheating to reaction temperature.Catalytic combustion reactor built with cellular noble metal catalyst, at bed air speed 20000h
-1, under the condition that inlet temperature is 330 DEG C, the pollutant in waste gas is fully oxidized, and purified gas enters caustic wash tower after entering heat exchanger heat exchange.Caustic wash tower is built with Pall ring filler, and alkaline absorption solution fully contacts with back flow of gas, HBr, Br in waste gas
2be absorbed by liquid absorption, comprise NaOH, sodium sulfite etc. in absorbing liquid, absorbing liquid recycles.Gas after alkali cleaning enters dry absorption facility, gas after super-dry process, a part of dry gas (about 20000 Nm
3/ h) for the blast system of device, all the other waste gas qualified discharge after off-gas expander recovers energy.
Through process, the total hydrocarbon concentration of purified gas is lower than 100mg/m
3, wherein benzene is less than 5mg/m
3, Bromofume is lower than 5mg/m
3, the concentration of carbon monoxide is lower than 10 μ L/L, HBr and Br
2do not detect.Through process, the whole qualified discharge of oxidized tail gas of PTA Equipment discharge.
Claims (7)
1. the purification method of p-phthalic acid's process gas, it is characterized in that comprising following content: the oxidized tail gas of p-phthalic acid's production process heats up through heat exchanger and preheater, then catalytic combustion reactor is entered, caustic wash tower is entered after catalytic combustion reactor outlet tail gas and inlet exhaust gases heat exchange, the tail gas of caustic wash tower discharge enters adsorption tower and carries out adsorption dry process, to avoid the harsh inlet air conditions meeting off-gas expander needed for the waste gas after catalytic combustion, discharge gas after dry process carries out reuse respectively, carry out energy regenerating, and wherein catalytic combustion system is identical with the pressure of p-phthalic acid's production process oxidized tail gas with caustic washing system pressure, be 0.7 ~ 1.2MPa, and adsorption dry facility is connected with catalytic combustion-alkali cleaning facility and is used, catalytic combustion-alkali cleaning facility is provided with bypass, when catalytic combustion-caustic washing system breaks down, bypass valve can be opened automatically, tail gas carries out adsorption dry process by original adsorption dry facility.
2. in accordance with the method for claim 1, it is characterized in that: the oxidized tail gas of p-phthalic acid's production process first through entrainment trap, and then carries out catalytic combustion process.
3. in accordance with the method for claim 1, it is characterized in that: in catalytic combustion reactor, be filled with honeycomb catalyst combustion catalyst, it supports precious metals pt, Pd and CeO
2active component.
4. in accordance with the method for claim 3, it is characterized in that: the entrance bed temperature of catalytic combustion reactor is 250 ~ 400 DEG C, and use space velocity range is 10000 ~ 50000h
-1.
5. in accordance with the method for claim 1, it is characterized in that: the signal that bypass valve is opened automatically, from the fault-signal of catalytic combustion-alkali cleaning facility, comprises the high limited signal of temperature of catalytic combustion reactor outlet, the fault-signal of alkali cleaning circulating pump.
6. in accordance with the method for claim 1, it is characterized in that: the absorbing liquid of caustic wash tower is containing two or more in NaOH, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium sulfite component.
7. in accordance with the method for claim 1, it is characterized in that: the adsorbent in adsorption tower is active carbon and silica gel, purified gas after an adsorption dry part is for the production of the blast system of device, and remaining waste gas to recover energy discharge through off-gas expander.
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| CN104033912A (en) * | 2014-06-18 | 2014-09-10 | 南京兰迪环保科技有限公司 | Device used for waste gas treatment and recycling |
| CN104096469A (en) * | 2014-07-24 | 2014-10-15 | 扬州荣康空气净化设备有限公司 | Complete purifying method for chemical industry waste gas |
| CN106076057A (en) * | 2016-08-19 | 2016-11-09 | 霍普科技（天津）股份有限公司 | A kind of organic waste gas catalytic combustion processing means |
| CN108906046A (en) * | 2018-07-17 | 2018-11-30 | 无锡威孚环保催化剂有限公司 | A kind of purified terephthalic tai-gas clean-up catalyst and preparation method |
| CN110508116B (en) * | 2019-09-19 | 2024-09-06 | 中节能工程技术研究院有限公司 | Waste circuit board smelting flue gas purification recovery system |
| CN113559694B (en) * | 2020-09-27 | 2024-09-03 | 刘莹莹 | Energy-saving and environment-friendly chemical waste gas treatment device |
| CN113996167B (en) * | 2021-11-04 | 2024-05-14 | 禾大西普化学（四川）有限公司 | Process and device for purifying and recycling oxidation reaction tail gas |
| CN114180520A (en) * | 2021-12-09 | 2022-03-15 | 四川天采科技有限责任公司 | Coproduction process for catalytic oxidation of PTA hydrogen extraction tail gas and hydrogen production from methanol |
Citations (2)
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| CN101301579A (en) * | 2008-06-20 | 2008-11-12 | 上海东化环境工程有限公司 | High-pressure tail gas treatment process in purified terephthalic acid |
| CN101637699A (en) * | 2008-08-02 | 2010-02-03 | 中国石油化工股份有限公司 | Method for purifying waste gas of pure terephthalic acid producing device |
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| JP4428818B2 (en) * | 2000-06-05 | 2010-03-10 | 株式会社日本触媒 | Waste gas treatment equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301579A (en) * | 2008-06-20 | 2008-11-12 | 上海东化环境工程有限公司 | High-pressure tail gas treatment process in purified terephthalic acid |
| CN101637699A (en) * | 2008-08-02 | 2010-02-03 | 中国石油化工股份有限公司 | Method for purifying waste gas of pure terephthalic acid producing device |
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