CN103768914B - A kind of acid water storage tank loss waste gas processing method - Google Patents
A kind of acid water storage tank loss waste gas processing method Download PDFInfo
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Abstract
The invention discloses a kind of acid water storage tank loss waste gas processing method, comprising: first the waste gas of (1) 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; (3) waste gas after distillate absorption enters organic amine absorption equipment, and rich amine solution enters amine liquid regenerative system; (4) waste gas after organic amine absorption enters alkali liquor absorption equipment, obtains purified gas after absorption.The present invention thoroughly can eliminate the environmental pollution that acid water storage tank loss waste gas produces, various pollution components in maximum recovery waste gas, be applicable to the air pollution control that oil refining enterprise's acid water storage tank produces, also can be used for the exhaust emission of the various sewage of type of industry and oil product storage tank generation, particularly containing the purification of high density sulfides waste gas.
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 of the various sewage of type of industry and oil product storage tank generation, particularly containing 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 of loss is complicated, and 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, by the environment of these Substances Pollution, may cause the diseases such as respiratory system, digestive system, reproductive system, also may cause body disease even carcinogenic; When short-term pollution is serious, people also can be made to produce the acute poisoning symptoms such as obvious dizziness, larynx pain, Nausea and vomiting.
Above-mentioned waste gas not only causes the odor pollution of surrounding enviroment, threatens to health, and causes a large amount of hydrocarbon resources to waste.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 kind of waste gas pollution control and treatment is also more and more urgent.
The process of malodorous waste gas discharged by storage tanks has its particularity, and main manifestations is, easily disturbs storage tank normally to run during emission-control equipment purifying exhaust air, as caused the flat tank of storage tank or quick-fried tank; In addition, tank discharge waste gas composition is complicated, and toxic emission time and discharge capacity are all uncertain, and purification difficulty is larger.
Adopt liquefied ammonia and high boiling organic solvent to absorb storage-tank waste gas in CN200610047790.4, the method can purifying exhaust air medium sulphide content and hydro carbons preferably, but the ammonia volatilized easily causes secondary pollution.Adopt liquefied ammonia in CN200710010373.7 and to purify waste water absorption storage-tank waste gas, the method can 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 purification storage-tank waste gas pollutant, the method adopts alkali lye to remove sulfide, then adopt combine adsorption bed adsorbs hydrocarbons, this pollutant can be purified well, but there is the longer problem of saturated hydrocarbons gas recovery process.
CN200710069125.X discloses a kind of heavy dirty oil tank stench exhaust gas treating method, the stench tail gas that blow device on heavy dirty oil pipeline comes first is cooled to 96 ~ 100 DEG C with air cooler, heavy dirty oil tank storage is sent to deposit, gas is drawn from heavy dirty oil tank, send into condenser cooling again, control temperature is below 50 DEG C, tail gas is carried out absorption deodorizing process with absorbent in absorption tower, deodorizing process is carried out again at venturi-type eductors absorbent, promote power, finally, by blow-down pipe by process after exhaust emissions.The method can effective purifying exhaust air medium sulphide content, but the 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 these methods above-mentioned, main technique adopts absorption process to purify sulfide, and main existing problems are that absorbent or alkali lye consumption are comparatively large, and operating cost is high, there is secondary pollution, and the limited floss hole that causes of purification efficiency still has odorant pollutant to discharge.Particularly when 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 DEG C;
(3) waste gas after distillate absorbs enters organic amine absorption equipment, and rich amine solution enters amine liquid regenerative system;
(4) waste gas after organic amine absorbs enters alkali liquor absorption equipment, obtains purified gas after absorption.
In the present invention, bleed equipment described in step (1) can adopt various forms of blower fan 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 claw vavuum pump, preferred helical-lobe compressor, liquid rotary compressor, liquid-ring vacuum pump or claw 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, adopts explosion-proof material etc. as adopted installation fire-proof motor or gas flow passage components.
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 significantly improves, but, too high pressure, supercharging equipment energy consumption can be made sharply to increase, and when gauge pressure is increased to more than 800KPa, the increase of pressure is not remarkable on assimilation effect raising impact.For the present invention, gauge pressure is 40 ~ 300KPa preferably, and within the scope of this, existing bleed equipment energy consumption is in more reasonably scope, and the absorption cleaning effect also highly significant of pollutant, 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 adjust 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 when tolerance is lower, can adopt atmospheric pressure device.
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 step ring.During absorption equipment employing absorption tower, the volume space velocity of waste gas is generally 20 ~ 1500h
-1, be preferably 500 ~ 1500h
-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, jet pump as new-type absorption equipments such as the reactor of power or inner circulation reactors, 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 select the thick cut oil product of various petroleum refining process, as one or more in gas-oil, raw gasoline, naphtha, boat coal etc. that still-process, catalytic cracking process, coking etc. produce, General Requirements initial boiling point is higher than 40 DEG C, preferably higher than 160 DEG C, absorbing temperature is-20 ~ 40 DEG C, preferably 0 ~ 15 DEG C.Concrete operations condition according to hydrocarbons content and the rate of recovery etc. in waste gas, can be determined by those skilled in the art, and the distillate absorbing waste gas enters downstream unit and carries out processing refinement.Low temperature absorption oil product freezes and other refrigeration modes by refrigerant cooling or electricity, and concrete mode is determined by those skilled in the art.Containing the more impurity such as organic sulfur compound, nitride in thick distillate, need further hydrotreatment just can obtain qualified product, not affecting character as hydrotreated feed for absorbing hydro carbons and organic sulfur compound after absorbent further in the present invention, saving device and the operating cost of lyosoption regeneration simultaneously.After being absorbed by distillate, recyclable more than the 95wt% of the hydro carbons in waste gas, recyclable more than the 99wt% of organic sulfur compound, recyclable more than the 90wt% of hydrogen sulfide.
In the present invention, absorbent in organic amine absorption equipment described in step (3) can select one or more in fatty amines, alcamines, amide-type, alicyclic ring amine, aromatic amine, naphthalene system amine, sulfone amine etc., 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 being absorbed by organic amine, hydrogen sulfide residual concentration is less than 400mg/m
3.
In the present invention, alkali liquor absorption process described in 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, recycle during operation, when 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, suitable additive can be added in desulfurization absorbing liquid, as the treatment effect in order to improve organic sulfur compound, small amounts agent can be added, there is the metallic compound etc. of catalytic action, as clorox, sulfonated phthalocyanine cobalt etc.After alkali liquor absorption, can 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 strict further, catalytic oxidation technologies or incineration technology can be taked to process further.
In the present invention, waste gas is by after bleed equipment pressure-raising-distillate absorption-organic amine absorption-alkali liquor absorption process, and 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 purification and the ability of recovery, and alkali lye consumption is larger.Adopt the present invention can reduce alkali lye and consume more than 96wt%, hydrocarbon recovery increases by 1 ~ 5 percentage point than ordinary-pressure absorption, and Absorbable organic halogens is at more than 95wt%, and after absorption, purified gas NMHC concentration Absorbable organic halogens is at 15000mg/m
3below, 5000 ~ 10000mg/m is reduced than ordinary-pressure absorption purified gas NMHC concentration
3above, day by day harsh exhaust of oil standard can be met.In addition, absorb after adopting bleed equipment pressure-raising, distillate consumption can be reduced over half, decrease the investment cost of supporting pipelines.
The present invention thoroughly can eliminate the environmental pollution that acidic storage tank loss waste gas produces, and farthest reclaims the various pollution components in waste gas, greatly reduces absorbent consumption and the secondary pollution of traditional treatment method.The inventive method is applicable to odor treatment and the hydro carbons recovery of all kinds of sulfur-and hydrocarbon-containing waste gas, 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-; 7-rich amine solution; 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.
Detailed description of the invention
Technical process of the present invention is further illustrated 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 compresses, and the rich distillate 6 after absorption is transported to downstream process units by rich oil pump 8.The pressure of distillate absorption equipment 3 regulates 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 solution 7 after absorption is transported to downstream unit by rich amine pump 9.Pressure in organic amine absorption equipment 4 regulates 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 regulates by pressure-control valve 15, and final purification gas 12 directly discharges.
Method of operating and the effect of the inventive method is further illustrated below by embodiment.
Embodiment 1
It is as shown in table 1 that certain enterprise's sour water storage tank distributes waste gas main odorant pollutant composition, and pressure is normal pressure.Adopt present invention process to purify, adopt liquid rotary compressor, make exhaust gas pressure be increased to gauge pressure 300KPa, working solution adopts the absorbent same with in distillate absorption equipment, adopt the gas-oil of boiling range 150 ~ 370 DEG C, absorption gauge pressure is 300KPa, and absorbing temperature is 10 DEG C.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 change fresh alkali lye when solution ph is down to 7.5.Distillate absorption equipment and organic amine absorption equipment adopt packed tower, and filling Dg25 metal Pall ring in tower, absorbent is 0.05 with exhaust gas volume ratio, and average exhaust gas volume space velocity is 1500h
-1.Alkali liquor absorption equipment adopts inner circulation reactor.In exhaust, various concentration of component is in table 1.
Table 1 embodiment 1 exhaust-gas treatment result
| Main malodorant kind | Concentration (mg/m before process 3） | Concentration (mg/m after process 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 10000mg/m
3, purifying rate reaches 99wt%.
Embodiment 2
It is as shown in table 2 that certain enterprise's sulfur-bearing storage tank distributes waste gas main odorant pollutant composition, and pressure is normal pressure.Adopt present invention process to purify, compressor adopts liquid rotary compressor, makes exhaust gas pressure be increased to gauge pressure 100KPa, working solution adopts the absorbent same with in distillate absorption equipment, adopt the gas-oil of boiling range 200 ~ 360 DEG C, absorption gauge pressure is 100KPa, and absorbing temperature is 0 DEG C.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, and filling Dg25 metal step ring in tower, absorbent is 0.07 with exhaust gas volume ratio, and average exhaust gas volume space velocity is 500h
-1.In exhaust, various concentration of component is in table 2.
Table 2 embodiment 2 exhaust-gas treatment result
| Main malodorant kind | Concentration (mg/m before process 3） | Concentration (mg/m after process 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 10000mg/m
3, purifying rate reaches 99wt%.
Comparative example 1
For the waste gas that same embodiment 2 is identical, waste gas, without pressure-raising, all adopts ordinary-pressure absorption.Distillate absorbent adopts the gas-oil of boiling range 200 ~ 360 DEG C, and absorbing temperature is 0 DEG C.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, and filling Dg25 metal step ring in tower, absorbent is 0.07 with exhaust gas volume ratio, and average exhaust gas volume space velocity is 500h
-1.In exhaust, various concentration of component is in table 3.
Table 3 comparative example exhaust-gas treatment result
| Main malodorant kind | Concentration (mg/m before process 3） | Concentration (mg/m after process 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 (14)
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 DEG C, and the absorption gauge pressure of distillate absorption equipment is 10 ~ 800KPa;
(3) waste gas after distillate absorbs enters organic amine absorption equipment, and the absorption gauge pressure of organic amine absorption equipment is 10 ~ 800Kpa, and rich amine solution enters amine liquid regenerative system;
(4) waste gas after organic amine absorbs enters alkali liquor absorption equipment, and the absorption gauge pressure of alkali liquor absorption equipment is 0 ~ 800KPa, obtains purified gas after absorption.
2. in accordance with the method for claim 1, it is characterized in that: the bleed equipment described in step (1) adopts helical-lobe compressor, liquid rotary compressor, liquid-ring vacuum pump or claw 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 40 ~ 300KPa, the absorption gauge pressure of alkali liquor absorption equipment is 0 ~ 300KPa.
6. according to the method described in claim 1 or 5, 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.
7. in accordance with the method for claim 6, it is characterized in that: 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.
8. in accordance with the method for claim 7, it is characterized in that: 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.
9. according to the method described in claim 1 or 5, it is characterized in that: described absorption equipment adopts hypergravity consersion unit, strengthening mass transfer stirred reactor, jet pump as the reactor of power or inner circulation reactor, and the time of staying of waste gas in absorption equipment is 0.1s ~ 20min.
10. according to the method described in claim 1 or 5, it is characterized in that: one or more in gas-oil, raw gasoline, naphtha, boat coal selected by the described distillate absorbent of step (2), and initial boiling point is higher than 40 DEG C.
11. in accordance with the method for claim 10, it is characterized in that: the initial boiling point of described absorbent is higher than 160 DEG C, and absorbing temperature is 0 ~ 15 DEG C.
12. in accordance with the method for claim 1, it is characterized in that: the organic amine absorbent described in step (3) selects one or more in monoethanolamine, diethanol amine, diisopropanolamine (DIPA), triethanolamine, N methyldiethanol amine.
13. in accordance with the method for claim 1, it is characterized in that: the alkali lye described in step (4) adopts the aqueous solution of NaOH and/or sodium carbonate, concentration is 0.1wt% ~ 30wt%, pH value is 7.5 ~ 14, recycle during operation, when pH value is down to below 7.5, adjust by changing or supplement fresh alkali lye.
14. in accordance with the method for claim 1, it is characterized in that: the purified gas described in step (4) directly discharges or take catalytic oxidation technologies or incineration technology to process further.
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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 |
| CN108114573B (en) * | 2016-11-29 | 2021-03-05 | 中国石油化工股份有限公司 | System and method for collecting, purifying and recycling tank top gas in storage tank area |
| CN108970349B (en) * | 2018-07-18 | 2021-04-27 | 武汉理工大学 | Marine diesel engine tail gas desulfurization and 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 |
| 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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| 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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