CN101028577A - Method for cryogenic cooling absorbing-regenerative oxidation recovery and treating oil air - Google Patents
Method for cryogenic cooling absorbing-regenerative oxidation recovery and treating oil air Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000001816 cooling Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims description 54
- 238000007254 oxidation reaction Methods 0.000 title claims description 54
- 238000011084 recovery Methods 0.000 title description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 87
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 42
- 230000001172 regenerating effect Effects 0.000 claims description 32
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 19
- 239000003502 gasoline Substances 0.000 claims description 14
- 238000004146 energy storage Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
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- 239000010935 stainless steel Substances 0.000 claims description 2
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Abstract
A method for recovering and treating the oil vapor generated during loading or unloading light oil by low-temp cooling-absorbing and oxidizing by accumulated heat includes such steps as absorbing the raw oil vapor by absorbing liquid and filler layer in absorption tower, heating in heat-accumulating oxidizing unit, high-temp oxidizing for decomposing to release a lot of heat, cooling by heat-accumulating bed, exhausting, and refrigerating by accumulated heat for cooling the absorbent.
Description
Technical field
The invention belongs to gas purification, solvent recovery, petrochemical industry.Be particularly related to light-end products and adorn/unload a kind of cryogenic cooling absorbing-regenerative oxidation recovery of the oil gas that produces in the process and the method for processing oil gas.
Technical background
The oil gas evaporation thing that petrochemicals are being adorned/unloaded, produce in the storage and transport process comprises volatile organic matters such as lighter hydrocarbons, benzene,toluene,xylene.The smell of evaporation oil gas often makes the people feel dizzy, and wherein benzene compounds is regarded as carcinogen by the expert.Suck a large amount of high concentration benzene vapors in the human body, can cause benzene poisoning.The lighter shows as excitement or intoxication, keep in dark place, shed tears, eye-blurred, and giddy, dizziness, headache are arranged, symptom such as feel sick, vomit, walk haltingly; Weight person goes into a coma, tic, blood pressure drops, so that breathe and circulatory failure; The concentration that sucks benzene is high more, the time is long more, and then degree of intoxication is more serious.
The oil gas evaporation that adorn/unload, storage and transport process produces can cause serious environmental to pollute, but and serious harm people's physical and mental health.And a series of photochemical reactions can take place with other pernicious gases in the air after being shone by ultraviolet ray in oil gas, form the bigger pollutant of toxicity.The loss of oil product had both caused the severe contamination of atmospheric environment, was again the significant wastage to the petroleum resources of preciousness.Therefore, the oil gas recycling that oil product is adorned/unloaded, produces in the storage and transport process is significant.
The technology that both at home and abroad oil gas is reclaimed and administers mainly contains condensation method, absorption process, absorption method, membrane separation process and firing method (thermal oxide, catalysis thermal oxide, regenerative oxidation and heat-storage catalytic oxidation) at present; Also have photocatalytic method, irradiation-induced degradation method and bioanalysis in addition.Can select different recycling technology according to composition, concentration, processing tolerance, emission request, operating cost and the scale of investment of oil gas different.Condensation method, absorption process, absorption method, membrane separation process all have the commercial Application case at home and abroad, ubiquitous problem be after handling gas or can not qualified discharge, perhaps up to standard but uneconomical reluctantly.Sub-cooled of the present invention absorbs with regenerative oxidation combination technique scheme characteristics: recovery section selects for use Processes and apparatus the simplest, the absorption process that economy is best, the optimization that absorbs operating condition also is to turn to target with economic maximum, the high regenerative oxidation method of low, the up to standard degree of depth of operating cost is selected in the processing of tail gas for use, by lithium bromide refrigerating the rich heat that produces in the oxidizing process is converted into cooling water simultaneously, absorbent is cooled off, improve organic efficiency.Therefore, new combined method is discharged the processing degree of depth height of gas, the resource utilization height to the good economy performance of Oil Recovery.
Summary of the invention
The objective of the invention is to propose the method that a kind of cryogenic cooling absorbing-regenerative oxidation reclaimed and handled oil gas.It is characterized in that described sub-cooled absorbs and the group technology of regenerative oxidation is divided into absorption, regenerative oxidation, three steps of lithium bromide refrigerating:
1) sub-cooled absorbs, and raw material oil gas at first enters the absorption tower, and adverse current constantly contacts with 7～12 ℃ absorption liquid, and behind packing layer, 70～90% oil gas is absorbed, and discharges from cat head;
2) regenerative oxidation, Residual oil gas after absorbing advances the regenerative oxidation section again to be handled, Residual oil gas is in the regenerative oxidation device, heat up gradually through energy storage bed, oxidation indoor temperature at oxidator reaches oxidation Decomposition under 500～800 ℃ of high temperature, again through another energy storage bed cooling, temperature is reduced to 35 ℃ to gas, qualified discharge after oxidizing chamber stops about 1～3 second; Residual oil gas can be emitted a large amount of heat in decompose the regenerative oxidation chamber, a part of heat is used to keep the temperature of oxidizing chamber, and other rich heat can be kept the temperature balance in the regenerative oxidation device like this by extraction.
3) lithium bromide refrigerating, 500～800 of extraction ℃ of high-temperature gases freeze by lithium bromide refrigerator as thermal source in the regenerative oxidation device, 7～9 ℃ of the cold water temperatures that produces return absorber portion again, reduce the absorption liquid temperature, sub-cooled absorbs, and therefore utilizes rich heat to improve the organic efficiency of oil product.
Described absorption liquid is kerosene, light diesel fuel or cold gasoline.
The filler of described packing layer is the stainless steel structured packing.
Described feedstock oil gas bag is drawn together the oil gas of gasoline, diesel oil, kerosene, benzene, dimethylbenzene, toluene, butanone generation.
The invention has the beneficial effects as follows that recovery method of the present invention is at the oil gas that reclaims and handle that light-end products are adorned/unloaded, produces in the storage and transport process, the processing degree of depth height of discharging gas, the resource utilization height, device is whole skid-mounted type equipment, floor space is little, simple, convenient, operating flexibility is big, and its comprehensive economy is very outstanding.To content of organics in the oil gas, to form accommodation wide, pollutant levels can satisfy national standard in the discharging gas.
Description of drawings
Fig. 1 reclaims and processing technological flow figure for sub-cooled absorbs with regenerative oxidation oil gas.
Among the figure: the Q01-spark arrester, the Q02-spark arrester, the Q03-spark arrester, the C01-absorption tower, R01-regenerative oxidation device,
The P01-pump, the P02-pump, E01-lithium bromide refrigerating device, the E02-cooler, the E03-cooler, the K01-blower fan,
The K02-blower fan, K03-blower fan, D01-air draft tube.
The specific embodiment
The present invention proposes the method that a kind of cryogenic cooling absorbing-regenerative oxidation reclaimed and handled oil gas.In sub-cooled absorption and recovery of regenerative oxidation oil gas and processing technological flow figure shown in Figure 1.Raw material oil gas at first passes through spark arrester (Q01), enters absorption tower (C01) from the bottom, absorption tower, and adverse current constantly contacts with absorption liquid, and behind packing layer, about 90% oil gas is absorbed.Residual oil gas after absorbing advances the regenerative oxidation section again to be handled.Residual oil gas heats up gradually through energy storage bed in regenerative oxidation device R01, then arrives oxidizing chamber oxidation Decomposition under 500～800 ℃ of high temperature, gas is after oxidizing chamber stops about 1～3 second, through another energy storage bed cooling, temperature can be reduced to about 35 ℃, qualified discharge again.Residual oil gas can be emitted a large amount of heat in decompose the regenerative oxidation chamber, a part of heat is used to keep the temperature of oxidizing chamber, and other rich heat is by extraction.Can keep the temperature balance in the regenerative oxidation device R01 like this, the heat of extraction can also utilize.The high-temperature gas of extraction is as thermal source in regenerative oxidation device R01, and by lithium bromide refrigerator E01 refrigeration, 7～9 ℃ of the cold water temperatures of generation, this part cold go the agent of absorber portion cooling and absorbing, and purpose is to utilize rich heat to improve the organic efficiency of oil product.Be a specific embodiment of the present invention below.
Embodiment 1
To contain benzene oil gas is example: oil gas through spark arrester (Q01), enters absorption tower (C01) from the bottom, absorption tower by the closed loading systematic collection, and temperature is a normal temperature, and pressure is 3000～5000Pa, and benzene concentration is about 180g/Nm
3(20 ℃).After the abundant counter current contacting of absorption liquid kerosene in absorption tower (C01) about, discharge from cat head with 10 ℃.The absorptivity of benzene goes out the about 18g/Nm of tower benzene concentration greater than 90% in the oil gas
3, 10～15 ℃ of temperature, the about 1000Pa of the pressure loss.Go out tower oil gas and enter the regenerative oxidation section through spark arrester (Q02) again, through the fresh air dilution of 5 times of air quantity, the about 4g/Nm of gas concentration
3, temperature is preheated by energy storage bed in regenerative oxidation device (R01) near normal temperature, and oil gas is oxidized fully in oxidizing chamber, and concentration is less than 10mg/Nm
3, 800 ℃ of temperature, gas is discharged through after another energy storage bed release heat after oxidizing chamber stops about 1.5 seconds, discharges the gas benzene concentration less than 15mg/Nm
3, 30～40 ℃ of temperature, the about 800Pa of the pressure loss.
Absorption liquid is that kerosene enters the absorption tower from storage tank behind pump (P01), flowmeter, cooler (E02), the about 1800kg/hr of flow, and about 10 ℃ of temperature behind the absorption benzene, is controlled through liquid level at the bottom of tower, and pump (P02) is sent the tank field back to.
Benzene is at oxidizing chamber internal reaction liberated heat, with 800 ℃ of gases as the carrier extraction, enter lithium bromide refrigerating device (E01), 7～9 ℃ of the cold water temperatures that produces, the temperature of tail gas is 200 ℃, tail gas is again after cooler (E03) is cooled to about 35 ℃, through air-introduced machine (K03), air draft tube (D01) discharging; Cooling water after cooler (E03) and tail gas heat exchange, returns refrigerator again through cooler (E02) and absorption liquid heat exchange.Fig. 1 is seen in technological process..
Embodiment 2
With gasoline oil gas is example: gasoline concentration is about 700g/Nm
3(20 ℃).In the absorption tower with about 10 ℃ the abundant counter current contacting of absorption liquid kerosene after, discharge from cat head.The absorptivity of gasoline goes out the about 140g/Nm of tower gasoline concentration greater than 80% in the oil gas
3Go out tower oil gas and enter the regenerative oxidation section through spark arrester (Q02) again, through the fresh air dilution of 10 times of air quantity, the about 14g/Nm of gas concentration
3, temperature is preheated by energy storage bed in regenerative oxidation device (R01) near normal temperature, and oil gas is oxidized fully in oxidizing chamber, and concentration is less than 100mg/Nm
3, 700 ℃ of temperature, gas is discharged through after another energy storage bed release heat after oxidizing chamber stops about 1.0 seconds, discharges gas gasoline concentration less than 120mg/Nm
3Subsequent process is with embodiment 1.
Embodiment 3
With butanone oil gas is example: gasoline concentration is about 130g/Nm
3(20 ℃).In the absorption tower with about 10 ℃ the abundant counter current contacting of absorption liquid kerosene after, discharge from cat head.The absorptivity of gasoline goes out the about 13g/Nm of tower gasoline concentration greater than 90% in the oil gas
3Go out tower oil gas and enter the regenerative oxidation section through spark arrester (Q02) again, through the fresh air dilution of 2 times of air quantity, the about 6.5g/Nm of gas concentration
3, temperature is preheated by energy storage bed in regenerative oxidation device (R01) near normal temperature, and oil gas is oxidized fully in oxidizing chamber, and concentration is less than 100mg/Nm
3, 700 ℃ of temperature, gas is discharged through after another energy storage bed release heat after oxidizing chamber stops about 2.5 seconds, discharges gas gasoline concentration less than 120mg/Nm3.Subsequent process is with embodiment 1.
Claims (7)
1. a cryogenic cooling absorbing-regenerative oxidation reclaims and handles the method for oil gas, it is characterized in that, the group technology that described sub-cooled absorbs with regenerative oxidation is divided into absorption, regenerative oxidation, three steps of lithium bromide refrigerating:
1) sub-cooled absorbs, and raw material oil gas at first enters the absorption tower, and adverse current constantly contacts with 7～12 ℃ absorption liquid, and behind packing layer, 70～90% oil gas is absorbed, and discharges from cat head;
2) regenerative oxidation, Residual oil gas after absorbing advances the regenerative oxidation section again to be handled, Residual oil gas is in the regenerative oxidation device, heat up gradually through energy storage bed, oxidation indoor temperature at oxidator reaches oxidation Decomposition under 500～800 ℃ of high temperature, and gas is after oxidizing chamber stops about 1～3 second, again through another energy storage bed cooling, temperature is reduced to 35 ℃, qualified discharge; Residual oil gas can be emitted a large amount of heat in decompose the regenerative oxidation chamber, a part of heat is used to keep the temperature of oxidizing chamber, and other rich heat can be kept the temperature balance in the regenerative oxidation device like this by extraction;
3) lithium bromide refrigerating, 500～800 of extraction ℃ of high-temperature gases freeze by lithium bromide refrigerator as thermal source in the regenerative oxidation device, 7～9 ℃ of the cold water temperatures that produces return absorber portion again, reduce the absorption liquid temperature, sub-cooled absorbs, and therefore utilizes rich heat to improve the organic efficiency of oil product.
2. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 1, it is characterized in that described absorption liquid is kerosene, light diesel fuel or cold gasoline.
3. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 1, it is characterized in that, described feedstock oil gas bag is drawn together the oil gas of gasoline, diesel oil, kerosene, benzene, dimethylbenzene, toluene, butanone generation.
4. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 1, it is characterized in that the filler of described packing layer is the stainless steel structured packing.
5. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 3, it is characterized in that the described taking back and process that contains benzene oil gas is an oxidation Decomposition under 800 ℃ of high temperature, gas stopped 1.5 seconds at oxidizing chamber.
6. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 3, it is characterized in that the taking back and process of described gasoline oil gas is an oxidation Decomposition under 700 ℃ of high temperature, gas stopped 1 second at oxidizing chamber.
7. reclaim and handle the method for oil gas according to the described cryogenic cooling absorbing-regenerative oxidation of claim 3, it is characterized in that the taking back and process of described butanone oil gas is an oxidation Decomposition under 700 ℃ of high temperature, gas stopped 2.5 seconds at oxidizing chamber.
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| CNB200610169699XA CN100482317C (en) | 2006-12-27 | 2006-12-27 | Method for cryogenic cooling absorbing-regenerative oxidation recovery and treating oil air |
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| CNB200610169699XA CN100482317C (en) | 2006-12-27 | 2006-12-27 | Method for cryogenic cooling absorbing-regenerative oxidation recovery and treating oil air |
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| CN101028577A true CN101028577A (en) | 2007-09-05 |
| CN100482317C CN100482317C (en) | 2009-04-29 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463023A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Segmental oil gas absorption recovering method |
| CN102809162A (en) * | 2012-08-08 | 2012-12-05 | 陈汉笙 | Flameless two-way thermal oxidizer |
| CN104096452A (en) * | 2014-07-11 | 2014-10-15 | 海湾环境科技（北京）股份有限公司 | Oil gas recovery process adopting cooling oil pre-absorption adsorption method |
| CN104096448A (en) * | 2014-07-11 | 2014-10-15 | 海湾环境科技（北京）股份有限公司 | Oil gas circulating recovery device |
| CN104548870A (en) * | 2014-12-31 | 2015-04-29 | 陈蔚峰 | Oil gas treatment system |
| CN105032112A (en) * | 2015-08-16 | 2015-11-11 | 常州大学 | Novel oil-gas recovery system adopting absorption-adsorption-condensation integrating technology |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2058108A1 (en) * | 1970-11-26 | 1972-05-31 | Ernst Huerner & Co Gmbh | Separating nitrogen oxides from off-gases - by absorption in soln |
| CN1522785A (en) * | 2003-09-04 | 2004-08-25 | 潘汉华 | Oil gas recovery method |
-
2006
- 2006-12-27 CN CNB200610169699XA patent/CN100482317C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463023A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Segmental oil gas absorption recovering method |
| CN102463023B (en) * | 2010-11-04 | 2014-01-01 | 中国石油化工股份有限公司 | Segmental oil gas absorption recovering method |
| CN102809162A (en) * | 2012-08-08 | 2012-12-05 | 陈汉笙 | Flameless two-way thermal oxidizer |
| CN102809162B (en) * | 2012-08-08 | 2016-03-30 | 陈汉笙 | The two-way thermal oxidizer of a kind of nonflame |
| CN104096452A (en) * | 2014-07-11 | 2014-10-15 | 海湾环境科技（北京）股份有限公司 | Oil gas recovery process adopting cooling oil pre-absorption adsorption method |
| CN104096448A (en) * | 2014-07-11 | 2014-10-15 | 海湾环境科技（北京）股份有限公司 | Oil gas circulating recovery device |
| CN104096448B (en) * | 2014-07-11 | 2016-09-07 | 海湾环境科技（北京）股份有限公司 | A kind of oil gas circulation and stress device |
| CN104548870A (en) * | 2014-12-31 | 2015-04-29 | 陈蔚峰 | Oil gas treatment system |
| CN104548870B (en) * | 2014-12-31 | 2017-05-03 | 陈蔚峰 | Oil gas treatment system |
| CN105032112A (en) * | 2015-08-16 | 2015-11-11 | 常州大学 | Novel oil-gas recovery system adopting absorption-adsorption-condensation integrating technology |
| CN105032112B (en) * | 2015-08-16 | 2018-10-19 | 常州大学 | A kind of gas recovery system for oil of absorption-adsorption-condensation integrated technology |
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| CN100482317C (en) | 2009-04-29 |
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Address after: 100084 Beijing 100084-82 mailbox Co-patentee after: Beijing Zhong Shi Da Energy Technology Co., Ltd. Patentee after: Tsinghua University Address before: 100084 Beijing 100084-82 mailbox Co-patentee before: Peking University Enterprise Corporation Oil and Gas Technology Application Institute Co., Ltd. Patentee before: Tsinghua University |
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Granted publication date: 20090429 Termination date: 20181227 |