CN102908884A - 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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- CN102908884A CN102908884A CN2011102174080A CN201110217408A CN102908884A CN 102908884 A CN102908884 A CN 102908884A CN 2011102174080 A CN2011102174080 A CN 2011102174080A CN 201110217408 A CN201110217408 A CN 201110217408A CN 102908884 A CN102908884 A CN 102908884A
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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 the waste gas purification field.This waste gas is from the oxidized tail gas that discharges in the 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 p-phthalic acid's production process, contain the 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, mostly discharging directly into atmosphere has not caused very large pollution to atmospheric environment to the oxidation gaseous effluent of its generation through effectively processing.
CN96195949.5 discloses a kind of p-phthalic acid's of containing tail gas at interior waste gas processing method.It comprises makes waste gas under high pressure carry out catalytic combustion, and the gas that will process is sent into energy-recuperation system, it is characterized by: can be transformed into the compound of gaseous bromine compound when containing original bromide or catalytic combustion in the waste gas streams, or in liquid phase to the compound of the manufactured materials of the energy-recuperation system effect of being corrosive; Contain the waste gas of above-mentioned original bromide through catalytic combustion; The gas of the gaseous bromine compound that contains follow-up generation after treatment enters energy-recuperation system; Controlled pressure and temperature conditions to prevent above-mentioned various bromide condensation occurs by energy-recuperation system the time, and by behind the energy-recuperation system, above-mentioned follow-up bromide are removed from the gas of processing.This method is a kind of HIGH PRESSURE TREATMENT technology, before advancing decompressor, processes in tail gas, tightr with the combination of process units, relatively be fit 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 this technology is directly adopted in the processing of its tail gas, the gas after catalytic combustion is processed goes the off-gas expander of process units to recover energy, and is difficult to satisfy the air inlet requirement of off-gas expander; And off-gas expander directly closely links to each other with process units, and expensive, if the off-gas expander that more renews certainly will cause the huge waste of resource, has improved again the vent gas treatment expense simultaneously.Therefore, concerning existing PTA Equipment, the described technology of CN96195949.5 also is not suitable for.
JP-A-559517 discloses a kind of high pressure catalytic combustion processing method of the p-phthalic acid's of processing tail gas, mainly is after utilizing catalytic combustion technology that tail gas is processed, gas discharging after energy reclaims after processing.Except it does not consider HBr, Br
2Processing outside, its handling process and the described flow process of patent CN96195949.5 are basically identical.This technology is not suitable for the vent gas treatment of existing process units equally.
The domestic pure terephthalic acid producing device of building in the past in 2000, its oxidized tail gas mostly do not have through effective processing and discharging directly into atmosphere.Oxidized tail gas mainly contains three whereabouts: see Fig. 3.Under the normal production conditions, except small part waste gas directly discharged by aiutage before adsorption tower, all the other waste gas carry out adsorption treatment through adsorption tower.Some is used for the device highpressure pneumatic system waste gas after adsorption tower is processed, and all the other waste gas recover energy through off-gas expander.Waste gas after the off-gas expander has 3 whereabouts: a part is used for device and presses blast system; 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 discharge by aiutage.In fact, this with the main purpose of single adsorption technology as the means of processing, it only is the blast system that is used for device in order to obtain dry inert gas, the organic component that is adsorbed in the adsorption process all is discharged in the atmosphere in the regenerative process of adsorption tower, atmosphere has been caused huge pollution, simultaneously, adsorption process for the carbon monoxide in the waste gas without any treatment effect.
To this organic exhaust gas that contains benzene, dimethylbenzene, acetic acid, methyl acetate, Bromofume, carbon monoxide etc., catalytic combustion is undoubtedly a kind of suitable processing method, 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 introduce all needs to replace adsorption tower, sets up high pressure catalytic combustion treating apparatus for the treatment of the oxidized tail gas of high pressure.These two kinds of technology are for newly-built PTA Equipment, be fit to, but for the existing PTA Equipment of not taking effective waste gas pollution control and treatment measure, because the waste gas behind the catalytic combustion need to satisfy the inlet air conditions of the harshness of off-gas expander, therefore, not only there is difficulty in technology and engineering, and has influence on the normal production of PTA Equipment; If supporting off-gas expander then makes the cost for the treatment of apparatus greatly increase again.
Therefore, concerning existing terephthalic acid production plant, the improvement technology that its vent gas treatment adopts, at first should satisfy the existing need of production of device, it is the air inlet requirement that treated purified gas will satisfy off-gas expander, do not affect the production of device, also will meet the discharge standard of country simultaneously, this just need to select suitable treatment technology 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 utilized the exhaust treatment system of existing apparatus, for the characteristics of p-phthalic acid's oxidized tail gas, under the condition that does not affect the process units running, the processing method of waste gas has been proposed.
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 enter catalytic combustion reactor, enter caustic wash tower after catalytic combustion reactor outlet tail gas and the heat exchange of entrance waste gas, the tail gas of caustic wash tower discharging enters adsorption tower and carries out the adsorption dry processing, and the discharging gas after dry the processing carries out respectively reuse, carries out the energy recovery.
In the inventive method, the oxidized tail gas of p-phthalic acid's production process can pass through first entrainment trap, and then carries out catalytic combustion and process.
In the inventive method, catalyticing combustion process can adopt catalytic combustion method of the prior art, is filled with cellular catalyst for catalytic combustion in the catalytic combustion reactor, supports precious metals pt, Pd and CeO on it
2The isoreactivity component.The entrance bed temperature scope of catalytic combustion reactor is generally 250～400 ℃, and using the air speed scope 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, need not change.Newly-built part comprises catalytic combustion system and caustic washing system.Catalytic combustion system and the pressure identical (disregard the pressure loss when flowing) of caustic washing system pressure with p-phthalic acid's production process oxidized tail gas are generally 0.7 ~ 1.2MPa.
The use of connecting with catalytic combustion-alkali cleaning facility of adsorption dry facility, 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 by original adsorption dry facility to be processed, guarantee the normal operation of process units blast system and off-gas expander, avoided the disastershutdown of process units.The automatic start signal of bypass valve is from the fault-signal of catalytic combustion-alkali cleaning facility, such as the high limited signal of temperature of catalytic combustion reactor outlet, the fault-signal of alkali cleaning circulating pump etc.
In the inventive method, the wind that the discharging gas after energy reclaims is further used for device send power.
In the processing method of the present invention, can make the discharging waste gas of existing PTA Equipment meet national standard, and take full advantage of the adsorption system of existing apparatus, on process units without any impact, energy-recuperation system is not needed any transformation, special under the condition of newly-built partial fault, can not affect the running of blast system and the off-gas expander of process units yet.Newly constructed facility can carry out construction under the condition that process units runs well, can not affect process units.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 can recover energy by off-gas expander, carry wind by the adsorption dry generation device, have good economic benefit, social benefit and environmental benefit.The inventive method is changed very little to existing PTA Equipment, can take full advantage of all devices of existing p-phthalic acid, invest lowlyer, is suitable for the oxidized tail gas processing of existing pure terephthalic acid producing device.
Description of drawings
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 lye storage tank, 7-circulating pump, 8-transfer valve group, the original adsorption system of 9-, 10-purified gas (discharging or reuse).
Fig. 2 is existing apparatus vent gas treatment schematic flow sheet.
Wherein: 1-oxidized tail gas (high pressure), 102-treating apparatus of the present invention on-position, the 103-adsorption tower, 104-off-gas expander, 105-aiutage, the in line waste gas of 106-, the 107-regeneration off gases, discharging waste gas behind the 108-decompressor, the import of 109-regeneration gas, the 110-high-pressure blast send and nitrogen system, presses wind to send among the 111-.
Fig. 3 is existing apparatus vent gas treatment FB(flow block).
The specific embodiment
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, through heating up behind heat exchanger and the preheater, waste gas after the intensification enters catalytic combustion reactor, is oxidized to carbon dioxide, water, HBr and Br
2, waste gas enters caustic wash tower subsequently, the HBr in the waste gas and Br
2By alkali liquor absorption, the purified gas major part that obtains goes the original adsorption system of device to carry out adsorption dry to process, and the purified gas part after the adsorption dry is for the production of the blast system of device, and remaining waste gas is through the off-gas expander discharging that recovers energy.
Exhaust-gas treatment flow process of the present invention is seen Fig. 1.
The pressure of oxidized tail gas pressure after entrainment trap of existing pure terephthalic acid producing device is 0.9MPa, about 200 ℃ of temperature.The present invention at first heats up waste gas through heat exchanger and heater, make its reaction temperature that reaches catalytic combustion, then enters catalytic combustion reactor, and under the effect of catalyst, organic component and carbon monoxide are oxidized to carbon dioxide, water, HBr and Br in the waste gas
2
Contain CO through removing in the gas after the catalytic combustion processing
2And H
2Outside the O, also contain HBr, Br
2, also need carry out alkali cleaning and process, to remove HBr and the Br that contains in the gas
2Filler is equipped with in caustic wash tower inside, and it provides mass transfer surfaces for solution-air in the tower two contacts, and this filler has larger specific area and good wetability, also has the advantages such as higher voidage, 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 the caustic wash tower bottom.Along with the consumption of alkali lye, the basicity of cleaning solution reduces gradually.Spent lye goes to the plant area sewage-farm to process.The absorption liquid of caustic wash tower mainly contains two or more in the components such as NaOH, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium sulfite.
Mainly contain N in the purified gas after the alkali cleaning
2, CO
2And H
2O, pollution components is thoroughly removed, and purified gas directly discharged and met discharging standards this moment.But also contain a large amount of water vapours in the purified gas of this moment, be not suitable for being directly used in the mass transport wind of device, also need to remove the mass transport that water vapour could be used for device afterwards through adsorption dry, could satisfy the air inlet requirement of off-gas expander.The present invention has utilized the original waste gas adsorption treatment facility of process units, purified gas is carried out adsorption dry process.The adsorbent that the adsorption dry facility adopts is active carbon and silica gel, mainly is purified gas to be carried out drying process.Gas part after adsorption dry is processed is for the production of the blast system of device, and remaining waste gas discharges atmosphere 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 seen Fig. 2, 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 that proposes according to the present invention as shown in Figure 1.Waste gas enters heat exchanger (heating) and heater after entrainment trap, waste gas enters catalytic combustion reactor after being preheating to reaction temperature.Cellular noble metal catalyst is housed, at bed air speed 20000h in the catalytic combustion reactor
-1, under the condition that inlet temperature is 330 ℃, the pollutant in the waste gas is by complete oxidation, and purified gas enters caustic wash tower after advancing the heat exchanger heat exchange.Pall ring filler is housed in the caustic wash tower, and alkaline absorption solution fully contacts with back flow of gas, the HBr in the waste gas, Br
2Be absorbed by liquid absorption, comprise NaOH, sodium sulfite etc. in the absorption liquid, absorption liquid recycles.Gas after the alkali cleaning enters dry absorption facility, gas after super-dry is processed, a part of dry gas (about 20000 Nm
3/ h) be used for the blast system of device, all the other waste gas qualified discharge after off-gas expander recovers energy.
Through processing, 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 processing the whole qualified discharges of oxidized tail gas of PTA Equipment discharging.
Claims (9)
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 enter catalytic combustion reactor, enter caustic wash tower after catalytic combustion reactor outlet tail gas and the heat exchange of entrance waste gas, the tail gas of caustic wash tower discharging enters adsorption tower and carries out the adsorption dry processing, and the discharging gas after dry the processing carries out respectively reuse, carries out the energy recovery.
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 passes through first entrainment trap, and then carries out catalytic combustion and process.
3. in accordance with the method for claim 1, it is characterized in that: be filled with cellular catalyst for catalytic combustion in the catalytic combustion reactor, support precious metals pt, Pd and CeO on it
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 ℃, and using the air speed scope is 10000～50000h
-1
5. in accordance with the method for claim 1, it is characterized in that: catalytic combustion system is identical with the pressure of p-phthalic acid's production process oxidized tail gas with caustic washing system pressure, is 0.7 ~ 1.2MPa.
6. in accordance with the method for claim 1, it is characterized in that: the use of connecting with catalytic combustion-alkali cleaning facility of adsorption dry facility, catalytic combustion-alkali cleaning facility is provided with bypass, when catalytic combustion-caustic washing system breaks down, bypass valve can be opened automatically, and tail gas carries out adsorption dry by original adsorption dry facility to be processed.
7. in accordance with the method for claim 6, it is characterized in that: the signal that bypass valve is opened automatically comprises the high limited signal of temperature of catalytic combustion reactor outlet, the fault-signal of alkali cleaning circulating pump from the fault-signal of catalytic combustion-alkali cleaning facility.
8. it is characterized in that in accordance with the method for claim 1: the absorption liquid of caustic wash tower contains two or more in NaOH, potassium hydroxide, magnesium hydroxide, sodium carbonate, the sodium sulfite component.
9. in accordance with the method for claim 1, it is characterized in that: the adsorbent in the adsorption tower is active carbon and silica gel, and the purified gas part after the adsorption dry is for the production of the blast system of device, and remaining waste gas is through the off-gas expander discharging that recovers energy.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110508116A (en) * | 2019-09-19 | 2019-11-29 | 中节能工程技术研究院有限公司 | Waste printed circuit board melting gas cleaning recovery system |
| CN113559694A (en) * | 2020-09-27 | 2021-10-29 | 陕西吾道天行信息科技有限公司 | Energy-concerving and environment-protective chemical waste gas's processing apparatus |
| CN113996167A (en) * | 2021-11-04 | 2022-02-01 | 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 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110508116A (en) * | 2019-09-19 | 2019-11-29 | 中节能工程技术研究院有限公司 | Waste printed circuit board melting gas cleaning recovery system |
| CN113559694A (en) * | 2020-09-27 | 2021-10-29 | 陕西吾道天行信息科技有限公司 | Energy-concerving and environment-protective chemical waste gas's processing apparatus |
| CN113996167A (en) * | 2021-11-04 | 2022-02-01 | 禾大西普化学（四川）有限公司 | Process and device for purifying and recycling oxidation reaction tail gas |
| 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 |
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