CN103768914A - Treatment method of dissipative exhaust gas from acidic water storage tank - Google Patents
Treatment method of dissipative exhaust gas from acidic water storage tank Download PDFInfo
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- CN103768914A CN103768914A CN201210404088.4A CN201210404088A CN103768914A CN 103768914 A CN103768914 A CN 103768914A CN 201210404088 A CN201210404088 A CN 201210404088A CN 103768914 A CN103768914 A CN 103768914A
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Abstract
The invention discloses a treatment method of dissipative exhaust gas from acidic water storage tank. The method includes the steps of: (1) increasing the pressure of dissipative exhaust gas from the acidic water tank top by air-entraining equipment to a gauge pressure of 0.1-800 KPa; (2) absorbing the exhaust gas with increased pressure in a distillate absorption device; (3) introducing the exhaust gas subjected to distillate absorption into an organic amine absorption device, and introducing the amine-enriched liquid into an amine regeneration system; and (4) introducing the exhaust gas subjected to organic amine absorption into an alkali liquor absorption device, so as to obtain purified gas after absorption. The invention can completely eliminate the environmental pollution caused by the dissipative exhaust gas from the acidic water storage tank, recover various kinds of pollution components from the exhaust gas by the maximum level, and is applicable to governance of pollution caused by the exhaust gas from the acid water storage tank in oil refineries, as well as to treatment of various sewages and exhaust gas from oil product storage tank in similar enterprises, and especially the purification of exhaust gas containing high-concentration sulfides.
Description
Technical field
The present invention relates to a kind of acid water storage tank loss waste gas processing method, be mainly used in the air pollution control that oil refining enterprise's acid water storage tank produces, also can be used for the exhaust emission that the various sewage of similar enterprise and oil product storage tank produce, particularly contain the purification of high density sulfides waste gas.
Background technology
Oil plant is in the process of processing crude oil, some facilities inevitably give off a large amount of odor pollution waste gas, as sour water storage tank, semi-finished product oil product storage tank, sump oil storage tank, particularly sour water storage tank, the waste gas component complexity of loss, in waste gas, odorant pollutant comprises hydrogen sulfide, organic sulfur compound, benzene homologues and other VOCs(volatile organic matter) etc. component.Staff's long term activity of earthquake, in the environment being polluted by these materials, may cause the diseases such as respiratory system, digestive system, reproductive system, also may cause body disease even carcinogenic; In the time that short-term pollution is serious, also can make the acute poisoning symptoms such as people produces obvious dizziness, larynx pain, feels sick, vomiting.
Above-mentioned waste gas not only causes the odor pollution of surrounding enviroment, health is threatened, and cause a large amount of hydrocarbon resources wastes.In the waste gas of acid water storage tank loss, various pollutant levels are high, and complicated components is difficult to thorough purification, and therefore the exploitation of this class waste gas pollution control and treatment is also more and more urgent.
The processing of malodorous waste gas discharged by storage tanks has its particularity, and main manifestations is when emission-control equipment purifying exhaust air, easily to disturb storage tank normally to move, as caused flat tank or the quick-fried tank of storage tank; In addition, storage tank discharging waste gas composition is complicated, and toxic emission time and discharge capacity are all uncertain, purify difficulty larger.
In CN200610047790.4, adopt liquefied ammonia and high boiling organic solvent to absorb storage-tank waste gas, the method is purifying exhaust air medium sulphide content and hydro carbons preferably, but the ammonia of volatilization easily causes secondary pollution.In CN200710010373.7, adopt liquefied ammonia and the absorption storage-tank waste gas of purifying waste water, the method is purifying exhaust air medium sulphide content preferably, but the ammonia of volatilization easily causes secondary pollution, and hydro carbons is not recycled.CN200710012210.2 adopts desulfurization-absorbing process to purify storage-tank waste gas pollutant, the method adopts alkali lye to remove sulfide, then adopt combine adsorption bed adsorbs hydrocarbons, can purify well this pollutant, but the problem that exists saturated hydrocarbons gas recovery process to grow.
CN200710069125.X discloses a kind of heavy slop tank stench exhaust gas treating method, the stench tail gas that heavy sump oil pipeline blowing up sweeping device is come is first cooled to 96～100 ℃ with air cooler, send heavy slop tank to store, draw gas from heavy slop tank, send into again condenser cooling, control temperature below 50 ℃, tail gas is absorbed to deodorizing processing with absorbent in absorption tower, carry out deodorizing processing in venturi-type eductors with absorbent again, promote power, finally, by blow-down pipe by exhaust emissions after treatment.The method is purifying exhaust air medium sulphide content effectively, but hydro carbons in waste gas is not purified, and in addition, after long time running, organic sulfur compound purification efficiency reduces comparatively obvious, and absorbent is changed frequent.
In above-mentioned these methods, main technique adopts absorption process to purify sulfide, and main existing problems are that absorbent or alkali lye consumption are larger, and operating cost is high, has secondary pollution, and the limited floss hole that causes of purification efficiency still has odorant pollutant discharge.Particularly, in the time processing the waste gas containing high-concentration hydrogen sulfide, organic sulfur and hydro carbons complex component of acid water storage tank loss, hydro carbons waste gas often can not be purified preferably.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of acid water storage tank loss waste gas processing method.The method can improve the rate of recovery of hydro carbons greatly, makes the pollution components such as various sulfide, hydro carbons in waste gas be recycled and purify, and reduces alkali lye or the consumption of absorbent and the disposal cost of useless absorbent, reduces the investment cost of supporting pipelines.
Acid water storage tank loss waste gas processing method of the present invention, comprises the steps:
(1) first the waste gas of acid water tank deck loss carry out pressure-raising through bleed equipment, and after pressure-raising, the gauge pressure of waste gas is 0.1～800KPa;
(2) waste gas after pressure-raising enters distillate absorption equipment and absorbs, and absorbing temperature is-20～40 ℃;
(3) waste gas after distillate absorbs enters organic amine absorption equipment, and rich amine liquid enters amine liquid regenerative system;
(4) waste gas after organic amine absorbs enters alkali liquor absorption equipment, after absorbing, obtains purified gas.
In the present invention, the described bleed equipment of step (1) can adopt various forms of blower fans or the pressure-raising equipment such as helical-lobe compressor, Lodz blower fan, liquid-ring vacuum pump, liquid rotary compressor, scroll vacuum pump, screw compressor, centrifugal compressor or pawl formula vavuum pump, preferably helical-lobe compressor, liquid rotary compressor, liquid-ring vacuum pump or pawl formula vavuum pump.The preferred recommendation liquid rotary compressor of the present invention, because liquid rotary compressor has good security.Above-mentioned bleed equipment preferably carries out Explosion-proof Design, as adopted installation fire-proof motor or gas flow passage components to adopt explosion-proof material etc.
In the present invention, waste gas is after bleed equipment pressure-raising, gauge pressure is increased to 0.1～800KPa, because waste gas is under malleation absorbs, absorption efficiency obviously improves, but, too high pressure, can make supercharging equipment energy consumption sharply increase, gauge pressure is increased to 800KPa when above, and it is not remarkable that the increase of pressure improves impact to assimilation effect.For the present invention, gauge pressure is 40～300KPa preferably, and within the scope of this, existing bleed equipment energy consumption is in more rational scope, the also highly significant of absorption cleaning effect of pollutant, and the purification efficiency of exhaust emission component all can reach 95wt%～99wt%.The absorption pressure of distillate absorption equipment and organic amine absorption equipment can be adjusted according to actual process, and absorption gauge pressure is 10～800KPa, and preferably absorbing gauge pressure is 40～300KPa.The absorption gauge pressure of alkali liquor absorption equipment is 0～800KPa, and preferably absorbing gauge pressure is 0～300KPa, generally, in the time that tolerance is lower, can adopt normal pressure equipment.
In the present invention, described absorption equipment is applicable to distillate absorption equipment, organic amine absorption equipment and alkali liquor absorption equipment.Absorption equipment can adopt structure and the operating condition of this area routine, and as adopted material filling type absorption tower, top, absorption tower is provided with pressure-control valve, and inner-tower filling material is conventional structured packing, preferable alloy structured packing, more preferably metal cascade ring.When absorption equipment adopts absorption tower, the volume space velocity of waste gas is generally 20 ~ 1500h
-1, be preferably 500 ~ 1500 h
-1, the volume ratio of absorbent and waste gas is generally 0.005 ~ 0.5, is preferably 0.01 ~ 0.1.Absorption equipment also can adopt revolving bed absorption reactor thermally, hypergravity consersion unit, strengthening mass transfer stirred reactor, the jet pump new-type absorption equipment such as reactor or inner circulation reactor as power, and the time of staying of waste gas in absorption equipment is 0.1s ~ 20min.
In the present invention, the absorbent of the distillate absorption equipment described in step (2) can be selected the thick cut oil product of various petroleum refining processes, one or more in the gas-oil that produces as still-process, catalytic cracking process, coking etc., raw gasoline, naphtha, boat coal etc., General Requirements initial boiling point is higher than 40 ℃, preferably higher than 160 ℃, absorbing temperature is-20～40 ℃, preferably 0～15 ℃.Concrete operations condition can, according to hydrocarbons content and the rate of recovery etc. in waste gas, be determined by those skilled in the art, and the distillate that absorbs waste gas enters downstream unit and processes refinement.Low temperature absorption oil product can pass through the cooling or electric refrigeration of refrigerant and other refrigeration modes, and concrete mode is determined by those skilled in the art.In thick distillate, contain the more impurity such as organic sulfur compound, nitride, need further hydrotreatment just can obtain qualified product, in the present invention, for further having absorbed hydro carbons after absorbent and organic sulfur compound does not affect the character as hydrotreated feed, saved device and the operating cost of lyosoption regeneration simultaneously.After absorbing by distillate, more than the recyclable 95wt% of hydro carbons in waste gas, more than the recyclable 99wt% of organic sulfur compound, more than the recyclable 90wt% of hydrogen sulfide.
In the present invention, it is one or more in amine, sulfone amine etc. that absorbent in organic amine absorption equipment described in step (3) can be selected fatty amines, alcamines, amide-type, alicyclic ring amine, aromatic amine, naphthalene, specifically can adopt monoethanolamine (MEA), diethanol amine (DEA), one or more in diisopropanolamine (DIPA) (DIPA), triethanolamine (TEA), N methyldiethanol amine (MDEA) etc.Preferred alcohols amine absorbent, as N methyldiethanol amine etc.After absorbing by organic amine, hydrogen sulfide residual concentration is less than 400mg/m
3.
In the present invention, the described alkali liquor absorption process of step (4) can adopt alkaline aqueous solution, ethanolamine solutions etc., generally can use the aqueous solution of NaOH and/or sodium carbonate, concentration is 0.1wt%～30wt%, pH value general control is 7.5 ~ 14, when operation, recycle, in the time that pH value is down to below 7.5, adjust by changing or supplement fresh alkali lye.In order to improve exhuast gas desulfurization pretreating effect, can in desulfurization absorption liquid, add suitable additive, as in order to improve the treatment effect to organic sulfur compound, can add a small amount of oxidant, there is the metallic compound of catalytic action etc., as clorox, sulfonated phthalocyanine cobalt etc.After alkali liquor absorption, the pollutant such as various sulfide and ammonia in purifying exhaust air completely, last purified gas directly discharges.
In the present invention, in purified gas, still there is the hydrocarbon compound of a small amount of concentration, can directly discharge according to existing discharging standards, if national standard is further strict, can take catalytic oxidation technology or incineration technology further to process.
In the present invention, after waste gas is processed by bleed equipment pressure-raising-distillate absorption-organic amine absorption-alkali liquor absorption, in waste gas, the pollutant such as various sulfide, hydro carbons is all recyclable, and overall recovery is greater than 95wt%.Traditional alkali lye and oxidant absorption process only can purify hydrogen sulfide and a small amount of organic sulfur compound, and to hydro carbons, without any purifying and recovery ability, and alkali lye consumption is larger.More than employing the present invention can reduce alkali lye consumption 96wt%, the hydro carbons rate of recovery absorbs and increases by 1～5 percentage point than normal pressure, and more than can being stabilized in 95wt%, after absorption, purified gas NMHC concentration can be stabilized in 15000mg/m
3below, reduce by 5000～10000mg/m than normal pressure absorption cleaning gas NMHC concentration
3above, can meet day by day harsh exhaust of oil standard.In addition, after employing bleed equipment pressure-raising, absorb, can reduce distillate consumption over half, reduced the investment cost of supporting pipelines.
The present invention can thoroughly eliminate the environmental pollution that acidic storage tank loss waste gas produces, and farthest reclaims the various pollution components in waste gas, has reduced greatly absorbent consumption and the secondary pollution of traditional treatment method.Odor treatment and hydro carbons that the inventive method is applicable to all kinds of sulfur-and hydrocarbon-containing waste gas reclaim, the particularly recycling of oil refining enterprise's acid water storage tank class waste gas.
Accompanying drawing explanation
Fig. 1 is a kind of waste-gas treatment process flow figure of the present invention.
Wherein: 1-waste gas; 2-compressor; 3-distillate absorption equipment; 4-organic amine absorption equipment; 5-alkali liquor absorption equipment; The rich distillate of 6-; The rich amine liquid of 7-; 8-rich oil pump; The rich amine pump of 9-; The poor distillate of 10-; The poor amine liquid of 11-; 12-purified gas; 13-distillate absorption equipment pressure-control valve; 14-organic amine absorption equipment pressure-control valve; 15-alkali liquor absorption equipment pressure-control valve.
The specific embodiment
Further illustrate technical process of the present invention below in conjunction with accompanying drawing.In the present invention, wt% is mass fraction.
As shown in Figure 1, tank top waste gas 1 enters distillate absorption equipment 3 and carries out counter-current absorption with the poor distillate 10 of low temperature after compressor 2 compressions, and the rich distillate 6 after absorption is transported to Downstream processing device by rich oil pump 8.The pressure of distillate absorption equipment 3 can regulate by pressure-control valve 13, and after distillate absorbs, waste gas enters organic amine absorption equipment 4 and carries out counter-current absorption with poor amine liquid 11, and the rich amine liquid 7 after absorption is transported to downstream unit by rich amine pump 9.Pressure in organic amine absorption equipment 4 can regulate by pressure-control valve 14, waste gas after absorption carries out desulfurization through alkali liquor absorption equipment 5 again, reaction pressure in alkali liquor absorption equipment 5 can regulate by pressure-control valve 15, and final purification gas 12 directly discharges.
Further illustrate method of operating and the effect of the inventive method below by embodiment.
Embodiment 1
It is as shown in table 1 that certain enterprise's sour water storage tank distributes the main odorant pollutant composition of waste gas, and pressure is normal pressure.Adopt technique of the present invention to purify, adopt liquid rotary compressor, make exhaust gas pressure be increased to gauge pressure 300KPa, working solution adopts and absorbent same in distillate absorption equipment, the gas-oil that adopts 150～370 ℃ of boiling ranges, absorption gauge pressure is 300KPa, absorbing temperature is 10 ℃.The absorption gauge pressure of organic amine absorption equipment is 250KPa, and the absorbent of employing is MDEA.The absorption gauge pressure of alkali liquor absorption equipment is 200KPa, and alkali lye uses 10wt% sodium hydrate aqueous solution, supplements and change fresh alkali lye in the time that pH is down to 7.5.Distillate absorption equipment and organic amine absorption equipment adopt packed tower, filling Dg25 metal Pall ring in tower, and absorbent is 0.05 with exhaust gas volume ratio, average exhaust gas volume air speed is 1500h
-1.Alkali liquor absorption equipment adopts inner circulation reactor.In exhaust, various concentration of component are in table 1.
Table 1 embodiment 1 exhaust-gas treatment result
| Main malodorant kind | Concentration (mg/m before processing 3） | Concentration (mg/m after processing 3） |
| Hydrogen sulfide | 150000 | <1 |
| Organic sulfur compound | 100~1500 | <1 |
| NMHC | 1000000 | 10000 |
As shown in Table 1, hydrogen sulfide and the nearly 100wt% of organic sulfur compound purifying rate, the NMHC concentration of outlet is 10000 mg/m
3, purifying rate reaches 99wt%.
Embodiment 2
It is as shown in table 2 that certain enterprise's sulfur-bearing storage tank distributes the main odorant pollutant composition of waste gas, and pressure is normal pressure.Adopt technique of the present invention to purify, compressor adopts liquid rotary compressor, makes exhaust gas pressure be increased to gauge pressure 100KPa, working solution adopts and absorbent same in distillate absorption equipment, the gas-oil that adopts 200～360 ℃ of boiling ranges, absorption gauge pressure is 100KPa, absorbing temperature is 0 ℃.The absorption gauge pressure of organic amine absorption equipment is 80KPa, and the absorbent of employing is DEA.The absorption gauge pressure of alkali liquor absorption equipment is 50KPa, and alkali lye uses the aqueous sodium carbonate of 10wt%.Distillate absorption equipment, organic amine absorption equipment and alkali liquor absorption equipment all adopt packed tower, filling Dg25 metal cascade ring in tower, and absorbent is 0.07 with exhaust gas volume ratio, average exhaust gas volume air speed is 500h
-1.In exhaust, various concentration of component are in table 2.
Table 2 embodiment 2 exhaust-gas treatment results
| Main malodorant kind | Concentration (mg/m before processing 3） | Concentration (mg/m after processing 3） |
| Hydrogen sulfide | 50000 | <0.5 |
| Organic sulfur compound | 100~1500 | <1 |
| NMHC | 300000 | 10000 |
As shown in Table 2, hydrogen sulfide and the nearly 100wt% of organic sulfur compound purifying rate, the NMHC concentration of outlet is 10000 mg/m
3, purifying rate reaches 99wt%.
Comparative example 1
For the identical waste gas of same embodiment 2, waste gas, without pressure-raising, all adopts normal pressure to absorb.Distillate absorbent adopts the gas-oil of 200～360 ℃ of boiling ranges, and absorbing temperature is 0 ℃.Organic amine absorbent is DEA, and alkali lye adopts 10wt% aqueous sodium carbonate.Distillate absorption equipment, organic amine absorption equipment and alkali liquor absorption equipment all adopt packed tower, filling Dg25 metal cascade ring in tower, and absorbent is 0.07 with exhaust gas volume ratio, average exhaust gas volume air speed is 500h
-1.In exhaust, various concentration of component are in table 3.
Table 3 comparative example exhaust-gas treatment result
| Main malodorant kind | Concentration (mg/m before processing 3） | Concentration (mg/m after processing 3） |
| Hydrogen sulfide | 50000 | <0.5 |
| Organic sulfur compound | 100~1500 | <1 |
| NMHC | 300000 | 20000 |
As shown in Table 3, hydrogen sulfide and the nearly 100wt% of organic sulfur compound purifying rate, the NMHC concentration of outlet is 20000mg/m
3.
Claims (15)
1. an acid water storage tank loss waste gas processing method, comprises the steps:
(1) first the waste gas of acid water tank deck loss carry out pressure-raising through bleed equipment, and after pressure-raising, the gauge pressure of waste gas is 0.1～800KPa;
(2) waste gas after pressure-raising enters distillate absorption equipment and absorbs, and absorbing temperature is-20～40 ℃;
(3) waste gas after distillate absorbs enters organic amine absorption equipment, and rich amine liquid enters amine liquid regenerative system;
(4) waste gas after organic amine absorbs enters alkali liquor absorption equipment, after absorbing, obtains purified gas.
2. it is characterized in that in accordance with the method for claim 1: the described bleed equipment of step (1) adopts helical-lobe compressor, liquid rotary compressor, liquid-ring vacuum pump or pawl formula vavuum pump.
3. according to the method described in claim 1 or 2, it is characterized in that: bleed equipment carries out Explosion-proof Design, adopt installation fire-proof motor or gas flow passage components to adopt explosion-proof material.
4. according to the method described in claim 1 or 2, it is characterized in that: after bleed equipment pressure-raising, the gauge pressure of waste gas is 40～300KPa.
5. in accordance with the method for claim 1, it is characterized in that: the absorption gauge pressure of distillate absorption equipment and organic amine absorption equipment is 10～800KPa, the absorption gauge pressure of alkali liquor absorption equipment is 0～800KPa.
6. in accordance with the method for claim 1, it is characterized in that: the absorption gauge pressure of distillate absorption equipment and organic amine absorption equipment is 40～300KPa, the absorption gauge pressure of alkali liquor absorption equipment is 0～300KPa.
7. according to the method described in claim 1,5 or 6, it is characterized in that: described absorption equipment adopts material filling type absorption tower, and top, absorption tower is provided with pressure-control valve, and inner-tower filling material is metal structured packing.
8. it is characterized in that in accordance with the method for claim 7: the volume space velocity 20 ~ 1500h of the waste gas on described absorption tower
-1, the volume ratio of absorbent and waste gas is 0.005 ~ 0.5.
9. it is characterized in that in accordance with the method for claim 8: the volume space velocity 500 ~ 1500h of the waste gas on described absorption tower
-1, the volume ratio of absorbent and waste gas is 0.01 ~ 0.1.
10. according to the method described in claim 1,5 or 6, it is characterized in that: described absorption equipment adopts hypergravity consersion unit, strengthening mass transfer stirred reactor, jet pump reactor or the inner circulation reactor as power, and the time of staying of waste gas in absorption equipment is 0.1s ~ 20min.
11. according to the method described in claim 1,5 or 6, it is characterized in that: the described distillate absorbent of step (2) is selected one or more in gas-oil, raw gasoline, naphtha, boat coal etc., and initial boiling point is higher than 40 ℃.
12. in accordance with the method for claim 11, it is characterized in that: the initial boiling point of described absorbent is higher than 160 ℃, and absorbing temperature is 0～15 ℃.
13. in accordance with the method for claim 1, it is characterized in that: the described organic amine absorbent of step (3) is selected one or more in monoethanolamine, diethanol amine, diisopropanolamine (DIPA), triethanolamine, N methyldiethanol amine etc.
14. in accordance with the method for claim 1, it is characterized in that: the described alkali lye of step (4) adopts the aqueous solution of NaOH and/or sodium carbonate, concentration is 0.1wt%～30wt%, pH value is 7.5 ~ 14, when operation, recycle, in the time that pH value is down to below 7.5, adjust by changing or supplement fresh alkali lye.
15. in accordance with the method for claim 1, it is characterized in that: the described purified gas of step (4) directly discharges or takes catalytic oxidation technology or incineration technology further to process.
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| CN108114573A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The collection and purification recovery system and method for a kind of tank area head space gas |
| CN108970349A (en) * | 2018-07-18 | 2018-12-11 | 武汉理工大学 | Boat diesel engine tail gas desulfurization denitrification integrated device and method |
| CN112896833A (en) * | 2019-12-04 | 2021-06-04 | 中国石油化工股份有限公司 | Storage tank exhaust emission reduction system and method |
| CN112999863A (en) * | 2021-02-22 | 2021-06-22 | 中国石油天然气股份有限公司 | Composite air purifying agent for oil field operation station and preparation and use methods thereof |
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| CN202336287U (en) * | 2011-11-10 | 2012-07-18 | 中国石油化工股份有限公司 | Integrated treatment system of organic waste gases of refining company |
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| CN102309914A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Treatment method for stinky waste gas discharged by storage tank |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107970735A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | The processing method and desulfuration adsorbent regeneration method for the tail gas that regenerative sulfur binding adsorbent produces |
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| CN108970349B (en) * | 2018-07-18 | 2021-04-27 | 武汉理工大学 | Integrated device and method for desulfurization and denitrification of marine diesel engine exhaust |
| CN112896833A (en) * | 2019-12-04 | 2021-06-04 | 中国石油化工股份有限公司 | Storage tank exhaust emission reduction system and method |
| CN112999863A (en) * | 2021-02-22 | 2021-06-22 | 中国石油天然气股份有限公司 | Composite air purifying agent for oil field operation station and preparation and use methods thereof |
| CN112999863B (en) * | 2021-02-22 | 2023-02-10 | 中国石油天然气股份有限公司 | Composite air purifying agent for oil field operation station and preparation and use methods thereof |
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