CN101301580A - Tail gas treatment process of butane method maleic anhydride device - Google Patents
Tail gas treatment process of butane method maleic anhydride device Download PDFInfo
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- CN101301580A CN101301580A CNA2008100393151A CN200810039315A CN101301580A CN 101301580 A CN101301580 A CN 101301580A CN A2008100393151 A CNA2008100393151 A CN A2008100393151A CN 200810039315 A CN200810039315 A CN 200810039315A CN 101301580 A CN101301580 A CN 101301580A
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- tail gas
- maleic anhydride
- catalyst
- treatment process
- oxidation reactor
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Abstract
The present invention discloses a treatment technique for vent gas of butane method maleic anhydride device. Vent gas of maleic anhydride is mixed with air after pre-treatment by washing tower and heated by heater; then catalytic oxidation reaction is performed on the mixed gas adopting noble metal honeycomb catalyst in catalytic oxidation reactor with entrance temperature at 100-450 DEG C and exit temperature at 350-750 DEG C, under pressure of 0-30 kPa(G); transforms harmful and volatile organic matter into carbon dioxide and water; finally is exhausted into atmosphere after heat recovery in vent gas heat exchanger. The present invention has advantages as follows: preventing catalyst phosphorism by eliminating influence of phosphorus in vent gas to catalyst adopting vent gas washing tower washing and adsorbent bed adsorption technology; having simple catalytic oxidation technique, small system resistance and low run cost because vent gas heat exchanger recovers reaction heat to heat feed vent gas in normal running course without additional fuel; having thorough vent gas treatment, no secondary pollution and detection result totally meeting with environment protection control request specified by national standard.
Description
Technical field
The present invention relates to a kind of in industrial production butane method maleic anhydride process tail gas treatment process, especially be catalytic oxidation technology.
Background technology
The cis-butenedioic anhydride production technology has two kinds of benzene method and butane methods.The main component of butane method maleic anhydride tail gas is nitrogen, oxygen, water vapour and carbon dioxide, contains contaminated environment harmful components such as a certain amount of carbon monoxide and benzene simultaneously.
Butane method maleic anhydride device tail gas generally adopts the directly discharging of the high point of chimney at present, and environment is caused severe contamination.Owing to contain the material that micro-phosphorus, sulphur etc. make catalyst poisoning in the butane method maleic anhydride device tail gas, therefore adopt common catalytic oxidation technology can not handle butane method maleic anhydride tail gas.
Also there is the part butane method maleic anhydride device to adopt thermal oxidation method such as heating power burning process and heat accumulation type thermal oxidation technology to handle tail gas in addition, but the shortcoming of heating power burning process and heat accumulation type thermal oxidation technology is to need to consume a large amount of fuel, operating cost is higher, and it is bigger to burn capacity, 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 be propose that a kind of technology is simple, SR is little, need not add auxiliary fuel, do not make catalyst poisoning, operating cost is low, the tail gas treatment process of butane method maleic anhydride device of non-secondary pollution, thorough tail gas treatment.
In order to achieve the above object, the technical scheme that adopts is: a kind of tail gas treatment process of butane method maleic anhydride device of proposition, it is characterized in that: cis-butenedioic anhydride tail gas at first enters water or the solution washing tower carries out preliminary treatment, remove the phosphorus in the tail gas, mix with air then, and heat with heater, enter catalyst oxidation reactor and carry out catalytic oxidation, the catalyst fixed bed noble metal honeycomb catalyst that is provided with of described catalyst oxidation reactor, at pressure 0～30kPa (G), inlet temperature is 100～450 ℃, outlet temperature is under 350～750 ℃ the condition, harmful volatile organic matter is converted into carbon dioxide and water, enters at last and enter atmosphere after heat is reclaimed in the tail gas heat exchanger heat exchange.
The inlet temperature of described catalyst oxidation reactor is preferably 300 ℃; Outlet temperature is preferably in below 700 ℃.
As the preferred technical solution of the present invention, cis-butenedioic anhydride tail gas preferably enters catalyst oxidation reactor with after air mixes after tail gas heat exchanger is heated to the catalyst initiation temperature.
Carry out the system's heater go into operation that heats up and to adopt steam heater or electric heater or oil burner or gas burner; Tail gas heat exchanger is preferably welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger.
As the preferred technical solution of the present invention, cis-butenedioic anhydride tail gas and air are mixed into before the catalyst oxidation reactor, at first remove remaining phosphorus through adsorbent bed, enter catalyst oxidation reactor then and carry out catalytic oxidation.After cis-butenedioic anhydride tail gas and Air mixing gas carry out catalytic oxidation, preferably enter and enter atmosphere after tail gas heat exchanger reclaims heat.
As another preferred version of the present invention, before entering tail gas heat exchanger, be introduced into the waste heat boiler heat exchange and reclaim heat from the purified gas of catalyst oxidation reactor outlet.
There is the bypass valve of a conditioned reaction device inlet temperature described catalyst oxidation reactor porch.
The part purified gas by circulating fan with enter tail gas heat exchanger again after cis-butenedioic anhydride tail gas mixes.
As catalytic oxidation mechanism of the present invention, following chemical reaction has mainly taken place in the catalyst oxidation reactor:
2C
4H
10+13O
2＝8CO
2+15H
2O+Q
2CO+O
2＝2CO
2+Q
C
2H
4O
2+2O
2＝2CO
2+2H
2O+Q
C
3H
4O
2+3O
2＝3CO
2+2H
2O+Q
Advantage of the present invention is: adopt efficient washing tail gas technology and tail gas adsorption technology thoroughly to eliminate in the cis-butenedioic anhydride tail gas phosphorus to the influence of catalyst, avoid catalyst poisoning, technology of the present invention is simple, volatile organic matter harmful in the butane method maleic anhydride device tail gas is converted into carbon dioxide and water, 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 butane method maleic anhydride tail gas, and system's energy stable operation; The catalyst that the present invention adopts, mechanical strength height, long service life, resistance are low; At last, the present invention adopts high-efficiency heat pipe heat exchanger, welded plate type heat exchanger and finned tube exchanger to reclaim reaction heat to add hot feed tail gas, need not additional fuel in the normal course of operation.
Description of drawings
Fig. 1 is the process chart of tail gas treatment process of butane method maleic anhydride device of the present invention;
Fig. 2 is the structural representation of the used catalyst oxidation reactor of technology of the present invention.
Wherein: 1 is water or solution washing tower; 2 is air-blaster; 3 is tail gas heat exchanger; 4 is heater; 5 is adsorbent bed; 6 is catalyst oxidation reactor; 7 is waste heat boiler; 8 is circulating fan; 9 is chimney; 10,11 is people's access hole; 12 is the gas access; 13 is gas vent; 14 is catalyst fixed bed layer.
The specific embodiment
Below in conjunction with drawings and Examples technology of the present invention is further elaborated.
Fig. 1 is the process chart of tail gas treatment process of butane method maleic anhydride device of the present invention, as seen from the figure: tail gas treatment process of butane method maleic anhydride device, it is characterized in that: cis-butenedioic anhydride tail gas at first enters water or solution washing tower 1 carries out preliminary treatment, remove the phosphorus in the tail gas, mix with air by air-blaster 2 then, and with heater 4 heating, enter catalyst oxidation reactor 6 and carry out catalytic oxidation, catalyst fixed bed layer 14 (Fig. 2) of described catalyst oxidation reactor 6 are equipped with the noble metal honeycomb catalyst, at pressure 0～30kPa (G), inlet temperature is 100～450 ℃, outlet temperature is under 350～750 ℃ the condition, harmful volatile organic matter is converted into carbon dioxide and water, enters at last and enter atmosphere after tail gas heat exchanger 3 reclaims heat.Employee's access way when people's access hole 10,11 ties up to maintenance, internal cleaning among Fig. 2.
Described catalyst oxidation reactor 6 inlet temperatures are preferably 300 ℃, and outlet temperature is preferably below 700 ℃.
Cis-butenedioic anhydride tail gas enters before the catalyst oxidation reactor 6, and elder generation's process adsorbent bed 5 is dephosphorization once more, avoids catalyst phosphorism in the catalyst oxidation reactor 6.
Noble metal in the described noble metal catalyst is the combination of any one or two kinds of noble metals in platinum, the palladium.
Cis-butenedioic anhydride tail gas enters catalyst oxidation reactor 6 with after air mixes after tail gas heat exchanger 3 is heated to the catalyst initiation temperature.
Described tail gas heat exchanger 3 is welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger.Carry out heater 4 employing steam heater or electric heater or oil burner or the gas burners that system heats up and goes into operation.There is the bypass valve of a conditioned reaction device inlet temperature described catalyst oxidation reactor 6 porch.The part purified gas by circulating fan 8 with enter tail gas heat exchanger 3 again after cis-butenedioic anhydride tail gas mixes.
, before entering tail gas heat exchanger 3, be introduced into waste heat boiler 7 heat exchanges and reclaim heat from the purified gas of the gas vent 13 of catalyst oxidation reactor 6.
Tail gas among the embodiment derives from certain company's butane method maleic anhydride device, and working condition is as shown in table 1.
Embodiment 1
After being heated to 260 ℃ through electric heater 4 after tail gas and air mix, entering catalyst oxidation reactor 6 and carry out catalytic oxidation.Tail gas carries out catalytic oxidation on the honeycomb platinum that places catalyst fixed bed layer 14, palladium metal combination catalyst, keep catalyst oxidation reactor 6 internal pressures to be about 16kPa (G), temperature is about 570 ℃, harmful volatile organic matter is converted into carbon dioxide and water, and discharging a large amount of heat, cleaning of off-gas enters from gas vent 13 and enters the atmosphere after tail gas heat exchanger 3 reclaims heat; Or be introduced into waste heat boiler 7 heat exchanges recovery heat, enter again and enter atmosphere by chimney 9 after tail gas heat exchanger 3 reclaims heats.
Detect sending into the laboratory after the discharging gas sampling after handling, the content detection result of NMHC is as shown in table 2 in the cleaning of off-gas.
Certain company's butane method maleic anhydride device tail gas of table 1 is formed
| Exhaust gas component | Form (mol%) |
| N2 | 74.64 |
| CO | 1.16 |
| O2 | 14.07 |
| CO2 | 0.83 |
| H2O | 8.98 |
| N-C4 (normal butane) | 0.29 |
| Acetic acid | 0.02 |
| Acrylic acid | 0.01 |
| Add up to | 100 |
| Volume flow Nm3/h | 80000 |
| Temperature ℃ | 45 |
| Pressure kPa (G) | 20 |
Certain economizes environmental monitoring central station Monitoring Data and control index table 2
| The pollutant title | Concentration of emission | Concentration of emission evaluation criterion (mg/m 3) |
| NMHC | 101 | 120 |
Annotate: concentration of emission is repeatedly the mean value of sampling.
Embodiment 2
Catalyst oxidation reactor 6 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 6 internal pressures are about 5kPa (G), inlet temperature and are about 150 ℃, outlet temperature and are about 460 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 116mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 3
Catalyst oxidation reactor 6 adopts the honeycomb palladium metal catalysts, and catalyst oxidation reactor 6 internal pressures are about 10kPa (G), inlet temperature and are about 200 ℃, outlet temperature and are about 510 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 112mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 4
Catalyst oxidation reactor 6 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 6 internal pressures are about 14kPa (G), inlet temperature and are about 240 ℃, outlet temperature and are about 540 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 108mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 5
Catalyst oxidation reactor 6 adopts the honeycomb palladium metal catalysts, and catalyst oxidation reactor 6 internal pressures are about 15kPa (G), inlet temperature and are about 300 ℃, outlet temperature and are about 590 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 100mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 6
Catalyst oxidation reactor 6 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 6 internal pressures are about 22kPa (G), inlet temperature and are about 340 ℃, outlet temperature and are about 660 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 99mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 7
Catalyst oxidation reactor 6 adopts the honeycomb palladium metal catalysts, and catalyst oxidation reactor 6 internal pressures are about 25kPa (G), inlet temperature and are about 360 ℃, outlet temperature and are about 675 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 98mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 8
Catalyst oxidation reactor 6 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 6 internal pressures are about 28kPa (G), inlet temperature and are about 400 ℃, outlet temperature and are about 720 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 90mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Embodiment 9
Catalyst oxidation reactor 6 adopts the honeycomb palladium metal catalysts, and catalyst oxidation reactor 6 internal pressures are about 27kPa (G), inlet temperature and are about 380 ℃, outlet temperature and are about 710 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 92mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
Catalyst oxidation reactor 6 adopts the honeycomb platinum metal catalyst, and catalyst oxidation reactor 6 internal pressures are about 24kPa (G), inlet temperature and are about 440 ℃, outlet temperature and are about 750 ℃, and all the other are with embodiment 1.After testing, the content of NMHC is 89mg/m in the cleaning of off-gas
3, reach national discharge standard of air pollutants.
The test monitoring butane method maleic anhydride emission-control equipment of putting certain company is constructed and put into operation on probation at the scene, 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 maleic anhydride waste gas treating apparatus has been carried out the spot sampling monitoring checked and accepted, testing result satisfies the environment protection control requirements of national Specification fully.
Claims (10)
1, tail gas treatment process of butane method maleic anhydride device, it is characterized in that: cis-butenedioic anhydride tail gas at first enters water or solution washing tower (1) carries out preliminary treatment, mix with air then, and heat with heater (4), enter catalyst oxidation reactor (6) and carry out catalytic oxidation, the catalyst fixed bed layer (14) of described catalyst oxidation reactor (6) is equipped with the noble metal honeycomb catalyst, at pressure 0～30kPa (G), inlet temperature is 100～450 ℃, outlet temperature is under 350～750 ℃ the condition, harmful volatile organic matter is converted into carbon dioxide and water, enters at last and enter atmosphere by chimney (9) after heat is reclaimed in tail gas heat exchanger (3) heat exchange.
2, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: catalyst oxidation reactor (6) inlet temperature is preferably 300 ℃, and outlet temperature is preferably below 700 ℃.
3, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: cis-butenedioic anhydride tail gas enters catalyst oxidation reactor (6) before, earlier through adsorbent bed (5).
4, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: the noble metal in the described noble metal catalyst is the combination of any one or two kinds of noble metals in platinum, the palladium.
5, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: cis-butenedioic anhydride tail gas enters catalyst oxidation reactor (6) with after air mixes after tail gas heat exchanger (3) is heated to the catalyst initiation temperature.
6, tail gas treatment process of butane method maleic anhydride device according to claim 1 or 5 is characterized in that: described tail gas heat exchanger (3) is welded plate type heat exchanger or heat exchange of heat pipe or finned tube exchanger.
7, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: carry out heater (4) employing steam heater or electric heater or oil burner or gas burner that system heats up and goes into operation.
8, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: there is the bypass valve of a conditioned reaction device inlet temperature described catalyst oxidation reactor (6) porch.
9, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: the part cleaning of off-gas by circulating fan (8) with enter tail gas heat exchanger (3) again after cis-butenedioic anhydride tail gas mixes.
10, tail gas treatment process of butane method maleic anhydride device according to claim 1 is characterized in that: the cleaning of off-gas from catalyst oxidation reactor (6) outlet is entering tail gas heat exchanger (3) before, is introduced into waste heat boiler (7) heat exchange and reclaims heat.
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| CNA2008100393151A CN101301580A (en) | 2008-06-20 | 2008-06-20 | Tail gas treatment process of butane method maleic anhydride device |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341303A (en) * | 2013-06-09 | 2013-10-09 | 济南国海能源科技有限公司 | Oxidation treatment system for combustible tail gas and application thereof |
| CN105498526A (en) * | 2015-12-14 | 2016-04-20 | 天津市天环精细化工研究所 | Catalytic oxidation treatment device for off-gas generated in maleic anhydride production through benzene oxidizing method |
| CN105605595A (en) * | 2016-01-12 | 2016-05-25 | 北京化工大学 | Integrated purification method and system for industrial waste gas containing cyanogen, hydrocarbon and NOx |
| CN106563332A (en) * | 2016-10-18 | 2017-04-19 | 浙江理工大学 | Exhaust gas purifying treatment system |
| CN106669376A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for using butane oxidation tail gas |
| CN107433127A (en) * | 2017-08-01 | 2017-12-05 | 云南省贵金属新材料控股集团有限公司 | A kind of method and device of low heat value industrial tail gas catalyzing, oxidizing and purifying and energy utilization |
| CN108426242A (en) * | 2018-04-17 | 2018-08-21 | 上海四方锅炉集团工程成套股份有限公司 | A kind of maleic anhydride waste gas burning process and boiler system |
| CN109304202A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of nanocomposite of carbon coating transition metal and its application |
| CN109761940A (en) * | 2019-03-18 | 2019-05-17 | 淄博齐翔腾达化工股份有限公司 | Crude maleic anhydride continuous rectification apparatus and process |
-
2008
- 2008-06-20 CN CNA2008100393151A patent/CN101301580A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341303A (en) * | 2013-06-09 | 2013-10-09 | 济南国海能源科技有限公司 | Oxidation treatment system for combustible tail gas and application thereof |
| CN106669376A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for using butane oxidation tail gas |
| CN105498526A (en) * | 2015-12-14 | 2016-04-20 | 天津市天环精细化工研究所 | Catalytic oxidation treatment device for off-gas generated in maleic anhydride production through benzene oxidizing method |
| CN105605595A (en) * | 2016-01-12 | 2016-05-25 | 北京化工大学 | Integrated purification method and system for industrial waste gas containing cyanogen, hydrocarbon and NOx |
| CN106563332A (en) * | 2016-10-18 | 2017-04-19 | 浙江理工大学 | Exhaust gas purifying treatment system |
| CN109304202A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of nanocomposite of carbon coating transition metal and its application |
| CN107433127A (en) * | 2017-08-01 | 2017-12-05 | 云南省贵金属新材料控股集团有限公司 | A kind of method and device of low heat value industrial tail gas catalyzing, oxidizing and purifying and energy utilization |
| CN107433127B (en) * | 2017-08-01 | 2020-04-21 | 云南省贵金属新材料控股集团有限公司 | Method and device for catalytic oxidation purification and energy utilization of low-calorific-value industrial tail gas |
| CN108426242A (en) * | 2018-04-17 | 2018-08-21 | 上海四方锅炉集团工程成套股份有限公司 | A kind of maleic anhydride waste gas burning process and boiler system |
| CN108426242B (en) * | 2018-04-17 | 2023-11-10 | 上海四方锅炉集团工程成套股份有限公司 | Maleic anhydride waste gas incineration process and boiler system |
| CN109761940A (en) * | 2019-03-18 | 2019-05-17 | 淄博齐翔腾达化工股份有限公司 | Crude maleic anhydride continuous rectification apparatus and process |
| CN109761940B (en) * | 2019-03-18 | 2024-03-26 | 淄博齐翔腾达化工股份有限公司 | Continuous rectifying device and process method for crude maleic anhydride |
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Open date: 20081112 |