CN101637699B - Method for purifying waste gas of pure terephthalic acid producing device - Google Patents
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Abstract
The invention discloses a method for purifying waste gas of a pure terephthalic acid producing device. Directly discharged waste gas of oxidation tail gas of the pure terephthalic acid device and waste gas discharged by an exhaust system are combined into stable waste gas, and the stable waste gas is taken as a basic treatment object of a catalytic combustion system and continuously enters the catalytic combustion system stably to maintain the continuous operation of the catalytic combustion system; and when the concentration of regeneration tail gas of an adsorption tower exceeds a control index, the tail gas enters the catalytic combustion system, and when the concentration of the regeneration tail gas of the adsorption tower is lower than the control index, the tail gas is directly discharged. The method adopts the normal-pressure catalytic combustion technology, performs concentration homogenization and mixing on the pure terephthalic acid waste gas at a tail end, and then orderly performs the catalytic combustion and alkali cleaning treatment. The flow adopted by the method changes the pure terephthalic acid device little, does not influence the production of the device, and is particularly suitable for environment-friendly improvement on the prior pure terephthalic acid device.
Description
Technical field
The present invention relates to a kind of purification method of waste gas, particularly from the purification method of discharging waste gas in p-phthalic acid's device production process.
Background technology
P-phthalic acid (PTA) is a kind of important chemical material.In the fine terephthalic acid production process; The waste gas that produces comprises two parts: a part is the oxidation gaseous effluent that contains benzene, xylenes, acetate, methyl acetate, Celfume, Bromofume that produces at oxidation stage, and another part is the gas extraction system exhaust gas discharged.Early stage most of p-phthalic acid's process units of building, mostly discharging directly into atmosphere has not caused very big pollution to atmospheric environment to its waste gas through effectively handling.Along with the increasingly stringent of national environmental protection rules, the waste gas that these devices produce needs effectively to handle the requirement that just can reach environmental regulation.
CN96195949.5 has introduced 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 handle is sent into energy-recuperation system; It is characterized by: can be transformed into the compound of gaseous state bromide when containing original bromide or catalytic combustion in the waste gas stream, or in liquid phase to the compound of the manufactured materials effect of being corrosive of energy-recuperation system; The waste gas that contains above-mentioned original bromide is through catalytic combustion; The gas of the gaseous state bromide that contains follow-up generation after treatment gets into energy-recuperation system; Controlled pressure and temperature conditions to prevent above-mentioned various bromide condensation takes place through energy-recuperation system the time, and through behind the energy-recuperation system, above-mentioned follow-up bromide are removed from the gas of handling.This method is a kind of HIGH PRESSURE TREATMENT technology;, handles in tail gas before advancing decompressor; With process units combine closelyr, relatively be fit to newly-built p-phthalic acid's device, waste gas catalytic combustion treating apparatus and process units design simultaneously, construction simultaneously, come into operation simultaneously.But for existing p-phthalic acid's device, if this technology is directly adopted in the processing of its tail gas, the gas after catalytic combustion is handled goes the tail gas decompressor of process units to recover energy, and can't satisfy the air inlet requirement of tail gas decompressor; And the tail gas decompressor directly closely links to each other with process units, and costs an arm and a leg, if change the tail gas decompressor that adapts to, certainly will cause the huge waste of resource, has improved the vent gas treatment expense simultaneously again.Therefore, concerning existing p-phthalic acid's device exhaust-gas treatment, the described method of CN96195949.5 also is not suitable for.
JP-A-559517 has also introduced 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 handled, and handles the discharging after energy reclaims of back gas.Except it does not consider HBr, Br
2Processing outside, the said flow process basically identical of its handling process and CN96195949.5.This technology is not suitable for the vent gas treatment of existing process units equally.And, patent CN96195949.5 and patent JP-A-559517 all just handled high pressure oxidized tail gas, can not handle the low pressure exhaust gas of gas extraction system discharging simultaneously.
Early stage most of p-phthalic acid's process units of building, its waste gas are not mostly through effectively handling and discharging directly into atmosphere.Generally adopt the processing mode of adsorption tower to do, use two adsorption tower handover operations, the adsorption tower regeneration gas is directly discharging still, and gross contamination emission does not reduce.Some is used for the device highpressure pneumatic system waste gas after adsorption tower is handled, and all the other waste gas recover energy through the tail gas decompressor.Waste gas after the tail gas decompressor 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 through the aiutage discharging; All the other most of waste gas are through the aiutage discharging.
To this organic exhaust gas that contains benzene, xylenes, acetate, methyl acetate, Celfume, Bromofume, catalytic combustion is undoubtedly a kind of only 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 is to replace adsorption tower, sets up the oxidized tail gas that high pressure catalytic combustion treating apparatus is used for handle high voltages, simultaneously supporting use high-temperature tail gas decompressor.These two kinds of technology can realize for newly-built p-phthalic acid's device.But for existing p-phthalic acid's device of not taking effective waste gas pollution control and treatment measure; Because supporting tail gas decompressor is a normal temperature tail gas decompressor; This decompressor can not adapt to the harsh conditions after the tail gas catalyzed burning; Therefore, not only on technology and engineering, there is difficulty, and has influence on the ordinary production of p-phthalic acid's device; If supporting again tail gas decompressor then makes the cost of treating apparatus increase greatly.
Summary of the invention
Deficiency to prior art; The invention provides a kind of processing method of p-phthalic acid's product gas; The inventive method has that technology is simple, equipment investment is low, to original production system and the little advantage of energy-recuperation system influence, be suitable for the processing of existing p-phthalic acid's product gas.
The present invention is through analyzing existing each strand of p-phthalic acid's process units waste gas, and oxidized tail gas discharges the gas allow compliance with emission standards after adsorption tower is handled.But in this system, in order to keep the stable operation of process units, oxidized tail gas needs directly discharging of part before adsorption tower, and this directly discharges gas and does not meet discharge standard.The regenerative process of adsorption tower adopts and continues regeneration in this system, and when an adsorption tower adsorption operations, another adsorption tower continues regeneration, and regeneration tail gas directly discharges, and this has just determined regeneration tail gas high in regeneration initial stage concentration, far surpasses discharge standard.But owing to be to continue regeneration, therefore in the regeneration tail gas of regeneration later stage discharging allow compliance with emission standards then.In addition, in p-phthalic acid's process units, also have the gas extraction system discharging waste gas, this exhaust gas flow and concentration are in a disguised form to stable.Therefore, suitable, the most most economical method is exactly only these three strands of waste gas to be handled.In these three strands of waste gas, in line gas and the gas extraction system discharging waste gas before the adsorption tower basicly stable (in the narration of back, close and be called stable waste gas); And regeneration off gases concentration fluctuates, and its NMHC concentration is from tens mg/m
3To several ten thousand mg/m
3Not etc., and since two adsorption towers cut in the operating operation process, during a tower adsorption operations, another tower keeps reproduced state always, this just determined regeneration a period of time after, pollutant levels have been low to moderate and have satisfied discharge standard in the regeneration tail gas.Problems such as stability, energy consumption are had higher requirement when therefore, regeneration tail gas being carried out the catalytic combustion processing.
Exhaust gas purifying method of the present invention comprises following content: the in line waste gas and the gas extraction system discharging waste gas of p-phthalic acid's device oxidized tail gas are combined into stable waste gas; Stablize waste gas and oxidized tail gas adsorption tower regeneration tail gas carries out the concerted catalysis burn processing; Concerted catalysis burn processing detailed process is: stablize the basic handling object of waste gas as catalytic combustion system; Get into the catalytic combustion treating apparatus continuously and stably, keep the catalytic combustion system continued operation; When adsorption tower regeneration tail gas concentration surpasses the control index, get into above-mentioned catalytic combustion treating apparatus, when adsorption tower regeneration tail gas concentration is lower than the control index, directly discharging.
In the exhaust gas purifying method of the present invention, adsorption tower regeneration tail gas concentration control index is generally confirmed according to environmental regulation, is the tail gas dual disposal after handling with catalytic combustion during owing to direct discharging, and therefore can control regeneration tail gas concentration is lower than 100～300mg/m
3In time, directly discharge.
In the exhaust gas purifying method of the present invention, catalytic combustion system adopts this area routine techniques to get final product, and general catalytic combustion reactor inlet temperature is 200～400 ℃, and air speed is 5000～100000h
-1Get into organic concentration control 1000～10000mg/m in the catalytic combustion reactor inlet gas
3When entering catalytic combustion reactor inlet gas organic concentration is low, replenish an amount of fuel; When entering catalytic combustion reactor inlet gas organic concentration is higher, replenish an amount of air.
The inventive method is put multiply waste gas to p-phthalic acid's production and is analyzed, and in conjunction with the original production apparatus features, has confirmed suitable exhaust-gas treatment scheme, has obtained following concrete technique effect.
1, need not change the original production device, ordinary production is not produced any influence.
2, the equipment that increases is less, only need increase a cover catalytic combustion system and relevant control device and get final product, and exhaust device is an atmospheric operation that equipment investment and operating cost all reduce greatly.Do not need equipment such as decompressor expensive in the original system are changed.
3, utilize the characteristics separately of p-phthalic acid's process units multiply waste gas, realize the normal running of emission-control equipment.With the basic handling object of waste gas more stable in the multiply waste gas as the catalytic combustion treatment technology, the stable normal running that can keep device for catalytic treatment, the problem of stopping when opening during the device of having avoided causing because of regeneration off gases is unstable.
4, to the lasting regeneration characteristics of p-phthalic acid's process units adsorption tower, when regeneration off gases coincidence control index, directly discharge, avoided the low concentration regeneration off gases to get into the problem that catalytic combustion system need replenish a large amount of fuel, reduced operating cost.After regeneration off gases is directly discharged, stablize waste gas entering catalytic combustion reactor, can keep the normal running of catalytic combustion system, do not need this device is stopped work, guaranteed the long period stable operation of device owing to still have.
5, stablize waste gas and mix the effect that can reach waste gas melting concn homogenizing, improved catalytic combustion treating apparatus operational stability with the unsettled regeneration off gases of concentration.
Description of drawings
Fig. 1 moves towards FB(flow block) for the existing various waste gas of p-phthalic acid's process units.
Fig. 2 is a kind of typical process of waste gas processing method of the present invention.
Fig. 3 is the original vent gas treatment flow chart of p-phthalic acid's device, wherein the on-position of the useless treatment technology of square frame position the present invention.
The specific embodiment
Exhaust-gas treatment schemes synthesis of the present invention has been considered the multiply waste gas that p-phthalic acid's process units produces; Employing is a catalytic combustion basic handling object to stablize waste gas; Simultaneously the unsettled adsorbent equipment regeneration off gases of concentration is introduced the catalytic combustion treating apparatus under different condition in good time, can the abundant purified treatment of waste gas can be kept the catalytic combustion system stable operation on the other hand on the one hand; Reduce postcombustion simultaneously, reduce running cost.
Exhaust-gas treatment flow process of the present invention is seen accompanying drawing 2.Three strands of pending waste gas get into heat exchanger in the buffering in-tank mixing, carry out heat exchange with the reactor outlet purified gas, get into then in the blending tank, through adding auxiliary fuel, make the exhaust gas concentration of blending tank outlet keep stable, to keep the stable of retort.Mixed waste gas gets in the catalytic combustion reactor, catalyst for catalytic combustion is housed, like noble metal catalyst or non-precious metal catalyst in the catalytic combustion reactor.Under the effect of catalyst for catalytic combustion, the pollution components in the waste gas is converted into CO
2, H
2O, HBr.Purified gas after the heat exchange cooling, gets into steam generator again in heat exchanger, recover energy, and tail gas further reduces temperature, gets into caustic wash tower then.The alkaline absorption solution of adverse current fully contacts with gas in the caustic wash tower, the HBr in the gas, Br
2By the alkaline absorption solution absorbing and removing, purified gas finally discharges.
Stablize the basic handling object of waste gas as device, the entering treating apparatus of continous-stable particularly switches under the emptying state in regeneration off gases, has risen and has kept the important function that catalytic combustion system runs well.Regeneration off gases is because fluctuation of concentration is bigger, and when concentration was higher, waste gas got into catalytic combustion system and handles, and when exhaust gas concentration was low, toxic emission was up to standard, and this moment, waste gas did not advance catalytic combustion system through the control of pneumatic operated valve, but discharging directly into atmosphere.Avoided the fluctuation of exhaust gas concentration through the variation of exhaust gas flow.
For guaranteeing the stable of blending tank outlet exhaust gas concentration, blending tank is provided with the auxiliary fuel inlet, controls the fuel flow rate that gets into blending tank automatically through automatic regulating valve.The auxiliary fuel that adds can be methyl alcohol, liquefied gas, Device in Gas etc., also can be near the high-concentration waste gas the device.The control valve of auxiliary fuel is according to unblanking, and this signal can be the temperature signal of catalytic combustion reactor outlet, also can be the concentration signal of blending tank.
Through the mix homogenizing, exhaust gas concentration obtains homogenizing, meets the inlet air conditions of catalytic combustion reactor, has guaranteed the stable of catalytic combustion reactor bed temperature.
The pretreated waste gas of homogenizing reaches uniform temperature behind heat exchanger and preheater, get into catalytic combustion reactor then, after being oxidized to carbon dioxide and water under the effect of catalyst.Being filled with cellular catalyst for catalytic combustion in the catalytic combustion reactor, is example with the precious metal catalyst combustion catalyst, supports precious metals pt, Pd and CeO on the catalyst
2The isoreactivity component.
Remove in the gas after catalytic combustion is handled and contain CO
2And H
2Outside the O, also contain HBr, Br
2Caustic wash tower is used for removing HBr and the Br that gas contains
2Filler is equipped with in caustic wash tower inside, and it provides mass transfer surfaces for solution-air two in the tower contacts, and this filler has bigger specific area and good wetability, also has advantages such as higher voidage, gas-flow resistance is little, corrosion-resistant, mechanical strength is big.Demist silk screen and filler are arranged at caustic wash tower top, to remove most of moisture content.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 handle.
Mainly contain CO in the purified gas after the alkali cleaning
2And H
2O meets discharging standards, qualified discharge.
Processing method of the present invention can make the discharging waste gas National standard of existing p-phthalic acid's device, and owing to handle (as shown in Figure 3) endways, process units had no influence.The device flow process is simple, and stable operation does not influence original process units, and purifying rate is high, non-secondary pollution, and investment cost is low, and waste heat can also utilize, and has good social benefit and environmental benefit.
Describe below in conjunction with the instance specific embodiments of the invention.
Certain existing p-phthalic acid's device, its original vent gas treatment flow process is seen Fig. 3, its toxic emission situation is respectively: the regeneration off gases 15000～20000m of adsorption tower
3/ h, waste gas total hydrocarbon concentration 100～15000mg/m
3In line waste gas 4000～5000m
3/ h, waste gas total hydrocarbon concentration 4000～8000mg/m
3Gas extraction system discharging waste gas 3000～6000m
3/, the dense 2000～6000mg/m of waste gas total hydrocarbon
3
The catalytic combustion handling process is as shown in Figure 2.In line exhaust gas pressure is higher before the absorption, after the pressure regulation automatic valve, directly gets into surge tank; The gas extraction system discharging waste gas is introduced surge tank through air-introduced machine; Directly get into surge tank when the concentration of regeneration off gases is higher, directly discharge through automatic regulating valve when concentration is low.After three strands of waste gas mix in surge tank, get into heat exchanger (heating) and heater, waste gas gets into catalytic combustion reactor after being preheating to reaction temperature.If the concentration of waste gas is on the low side, waste gas gets into blending tank through after the heat exchange, mixes with the auxiliary fuel that adds, and improves exhaust gas concentration, makes exhaust gas concentration satisfy the air inlet requirement of catalytic combustion reactor.The auxiliary fuel that adopts is a methyl alcohol.When the EGT of entering heater reaches reactor inlet temperature, do not heat, otherwise, be heated to the reactor inlet temperature that needs.Waste gas after the preheating gets into catalytic combustion reactor.Cellular noble metal catalyst is housed, at bed air speed 30000h in the catalytic combustion reactor
-1, under the condition that inlet temperature is 300 ℃, the pollutant in the waste gas after purified gas advances the heat exchanger heat exchange, again through a steam generator, is produced low-pressure steam by complete oxidation, recovers energy as far as possible.Get into caustic wash tower then.The 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 liquid and absorb the gas qualified discharge.Comprise NaOH, sodium sulfite etc. in the absorption liquid, absorption liquid recycles.
Through handling the whole qualified discharges of p-phthalic acid's process gas.Table 1 is the section processes data of catalytic combustion treating apparatus to waste gas.
Table 1 waste gas purification treatment effect
Claims (6)
1. the purification method of p-phthalic acid's process units waste gas; Comprise the steps: the in line waste gas and the gas extraction system discharging waste gas of p-phthalic acid's device oxidized tail gas are combined into stable waste gas; Stablize waste gas and oxidized tail gas adsorption tower regeneration tail gas carries out the concerted catalysis burn processing; Concerted catalysis burn processing process is: stablize the basic handling object of waste gas as catalytic combustion system, get into the catalytic combustion treating apparatus continuously and stably, keep the catalytic combustion system continued operation; When adsorption tower regeneration tail gas concentration surpasses the control index, get into above-mentioned catalytic combustion treating apparatus, when adsorption tower regeneration tail gas concentration is lower than the control index, directly discharging;
Wherein the in line waste gas of p-phthalic acid's device oxidized tail gas refers to the oxidized tail gas part that the needs part is directly discharged before adsorption tower, and the remainder of p-phthalic acid's device oxidized tail gas gets into adsorption tower;
Tail gas after catalytic combustion is handled after the heat exchange cooling, gets into steam generator again in heat exchanger, get into caustic wash tower then;
When entering catalytic combustion reactor inlet gas organic concentration is low, replenish an amount of fuel.
2. according to the described method of claim 1, it is characterized in that: adsorption tower regeneration tail gas concentration control index is: control regeneration tail gas concentration is lower than 100～300mg/m
3In time, directly discharge.
3. according to the described method of claim 1, it is characterized in that: the catalytic combustion reactor inlet temperature is 200～400 ℃, and air speed is 5000～100000h
-1
4. according to claim 1 or 3 described methods, it is characterized in that: get into organic concentration control 1000～10000mg/m in the catalytic combustion reactor inlet gas
3
5. according to the described method of claim 1, it is characterized in that: the alkaline absorption solution of adverse current contacts with gas in the caustic wash tower, the HBr in the gas, Br
2By the alkaline absorption solution absorbing and removing, purified gas finally discharges.
6. according to the described method of claim 1, it is characterized in that: catalytic combustion system uses noble metal catalyst or non-precious metal catalyst.
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Families Citing this family (12)
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| 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 |
| CN102580523A (en) * | 2011-01-05 | 2012-07-18 | 张家港市三星净化设备制造有限公司 | Organic waste gas concentrating, absorbing and catalyzing combustion 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 |
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| 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 |
| GB201417636D0 (en) * | 2014-10-06 | 2014-11-19 | Invista Tech Sarl | Production of an aromatic dicarboxylic acid |
| CN104566405B (en) * | 2014-12-05 | 2017-10-17 | 南京科技职业学院 | A kind of PTA oxidized tail gas catalysis burn processing method of low energy consumption |
| CN105570910A (en) * | 2016-01-19 | 2016-05-11 | 成都中科能源环保有限公司 | Catalytic combustion and waste heat utilization method for methane decarburized tail gas |
| CN105737173B (en) * | 2016-04-19 | 2018-03-13 | 西南化工研究设计院有限公司 | A kind of catalytic combustion system of purification organic waste gas treatment |
| CN106642165B (en) * | 2017-01-23 | 2021-06-29 | 中石化炼化工程（集团）股份有限公司 | Method for treating volatile organic compounds in refinery |
| CN107420922A (en) * | 2017-08-01 | 2017-12-01 | 中石化炼化工程（集团）股份有限公司 | The processing method of refinery's volatile organic matter |
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