CN101239271A - Cleaning treatment method of acid sewage storage tank discharging gas - Google Patents
Cleaning treatment method of acid sewage storage tank discharging gas Download PDFInfo
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- CN101239271A CN101239271A CNA2007100103737A CN200710010373A CN101239271A CN 101239271 A CN101239271 A CN 101239271A CN A2007100103737 A CNA2007100103737 A CN A2007100103737A CN 200710010373 A CN200710010373 A CN 200710010373A CN 101239271 A CN101239271 A CN 101239271A
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- storage tank
- drip washing
- stripping process
- sour water
- leacheate
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Abstract
The present invention provides a purifying treating method of sour water storage tank discharging, belonging to waste gas cleaning treatment field. The sour water storage tank discharging of the invention is purified via twice leaching, the first leaching employs segregating liquid of the segregating course rich in ammonia in the stripped process of the sour water, the second leaching employs purified water or industrial water from the stripped process of the sour water. The invention organical combination the stripped process of the sour water and the purifying treatment process of the sour water storage tank discharging, achieves perfect purifying treatment effect. Further, leaching liquid after being washing does not need other treating process and any outside material, can realizes closed circuit operation, and generate no effect to outsides. The invention has simple equipment, lower cost and has no potential safety hazard.
Description
Technical field
The present invention relates to a kind of purifying treatment method of acid sewage storage tank discharging gas, in particularly a kind of petroleum refining enterprise and the part petrochemical enterprise, the purifying treatment method of the acid sewage storage tank discharging gas of sulfur compound, ammonia.
Background technology
In petroleum refining enterprise and part petrochemical enterprise, can produce a kind of sour water that contains hydrogen sulfide, organic sulfur sulfide, ammonia, volatile organic matter pollutants such as (VOC), these sewage can't directly discharge, the general steam stripping that adopts is handled and recovery hydrogen sulfide and ammonia wherein, and purifying waste water behind the stripping can be used as the fresh water (FW) reuse or enter the sewage-farm and further handle discharging.
The sour water stripping generally can adopt double tower stripping flow process and single tower stripping flow process.Double tower stripping flow process such as US3335071, US3404072 etc., single tower stripping flow process such as US3518167, CN1059291A etc.The sour water stripping process is the very ripe technical process in present technique field, extensive use in enterprise.In double tower stripping flow process, it (mainly is H that the hydrogen sulfide column overhead is discharged sour gas
2S and CO
2), it (mainly is NH that the ammonia column overhead is discharged rich ammonia vapour
3And H
2O); In single tower stripping flow process, rich ammonia vapour is extracted out from side line, and cat head is discharged sour gas.The sour gas that stripping produces generally adopts claus process further to produce sulphur.Ammonia concentration is generally 10%～30% in the rich ammonia vapour that stripping produces, and can obtain the ammonia of higher degree through 2～3 grades of fractional condensation processes, and the branch lime set that contains finite concentration ammonia is returned the stripper inlet or mixed with pending sour water; Every grade of fractional condensation can be adopted different conditions in the fractional condensation process, to improve the rate of recovery of ammonia, as described in CN1059291A.The stripper bottom is discharged stripping and is purified waste water, and can be used as the fresh water (FW) reuse or advances the sewage-farm processing.Also can add appropriate bases in the stripping process, as NaOH etc., to improve the extracting rate of ammonia, as described in CN1205983A.
In petroleum refining and petrochemical enterprise, have multiple device and discharge sour water, generally these sour waters are collected to unify the stripping purified treatment.In order to keep the steady running of stripper plant, in sour water stripping process flow process, the bigger acid water pot of one or several volumes need be set, the unified storage of pending sour water, homogeneous.These sour water jars are generally atmospheric operation, pneumostome with atmosphere UNICOM is arranged, thereby [s such as pollutants in sewage such as ammonia, hydrogen sulfide, organic sulfur compound, VOC are known from experience and are dispersed in the atmosphere in a large number, the severe contamination surrounding environment, be detrimental to health the corrosion production equipment.
The purifying treatment method of the raw material water tank discharging gas of Daqing Petrochemical Company oil plant sulphur recovery workshop acidic water stripping device introduced in " petroleum refining and chemical industry " 2003 02 phase P15 " sulfur-bearing, contain the technological transformation of ammonia sewage jar exhaust deodorization " literary composition, and mainly adopting with the iron complexes is the desulfurizing agent adsorption desulfurize processing of main component.The iron complexes desulfurizing agent generally has removal effect preferably to sulfide, and is limited in one's ability to removing of other odorant pollutants such as ammonia.The more important thing is, because the factors such as variation of the inside and outside gas pressure of acid water storage tank, variations in temperature and liquid level, storage tank often is in certain " breathing " state, consequently oxygen concentration is higher in the storage tank discharging gas, and iron complexes absorbs the sulfide that will change iron behind the sulfide into, oxidation can take place in the sulfide of iron in the presence of oxygen, with spontaneous combustion, and then cause other security incident when serious.Therefore, this method has bigger potential safety hazard." petrochemical industry environmental protection " 2005 the 04th phase P32～33 " the airtight deodorizing of the acid water pot of sewage stripping " literary composition introduction is adopted two-stage to absorb and is handled, the discharging gas of the acid water pot of stripper plant of purifying waste water.Adopt special-purpose high-efficiency absorbent (unexposed composition), absorb by secondary eddy flow tower odorants such as hydrogen sulfide, mercaptan, thioether are removed, realize the tail gas qualified discharge.This method flow is comparatively complicated, needs to use special absorbent, and operating cost is higher, and the post processing of absorbent also is the problem that needs solve.
Summary of the invention
At the deficiencies in the prior art, the invention provides the purifying treatment method of the simple acid sewage storage tank discharging gas of a kind of flow process, in conjunction with the stripping process of sour water, provide a kind of purifying treatment method that can realize the acid sewage storage tank discharging gas of closed-circuit operation.
The purifying treatment method of acid sewage storage tank discharging gas of the present invention is on the basis of existing sour water stripping process, acid sewage storage tank discharging gas purifies through two-stage drip washing, storage tank discharging gas at first purifies through first order drip washing, and leacheate adopts the branch lime set of extracting ammonia fractional condensation process in the sour water stripping process out.The discharging gas that purifies through first order drip washing carries out second level drip washing purification, and leacheate is purifying waste water or water for industrial use of producing in the sour water stripping process.
In the inventive method, described sour water stripping process can be the double tower stripping process, also can be single tower stripping process.Because single tower stripping process equipment is simple, the preferred use.In the sour water stripping process, the fractional condensation process that stripper is extracted rich ammonia gas out generally adopts 2 grades or 3 grades.The method of operating of sour water stripping process and condition are contents well known to those skilled in the art.Sour water is generally from the hydrogenation plant of petroleum refining, PETROLEUM PROCESSING enterprise, often subtract in distillation pressure device, coking plant, the catalytic cracking unit etc. one or more.
In the inventive method, first order drip washing can be adopted arbitrary fraction lime set of fractional condensation process in the stripping process, also can be that what branch lime set is mixed use.If stripping process adopts 2 grades of fractional condensation, be leacheate preferably with second level branch lime set; If stripping process adopts 3 grades of fractional condensation, be leacheate preferably with the second level and/or third level branch lime set.First order drip washing can be adopted common equipment and mode of operation and condition.Absorption equipment can be selected Venturi absorber or packed tower etc. for use, and preferred filler tower, leacheate spray downwards from the packing layer top, and acid sewage storage tank discharging gas can pass through packing layer from the top down, also can pass through packing layer from bottom to top.Leacheate can once pass through packed tower, also can all or part ofly recycle, and can replenish the branch lime set in the stripping process when recycling when leacheate pH value is reduced to certain limit continuously or off and on.Can also add the alkaline matter of other type in the leacheate, as NaOH, sodium carbonate etc., addition is advisable not influence the stripper normal running.The leacheate of discharging can enter acid sewage storage tank, also can enter stripper, preferably the former.First order drip washing mainly utilizes and contains certain density ammonia in the branch lime set, fully absorbs odorants such as hydrogen sulfide in the storage tank discharging gas, organic sulfur compound, and removes the part hydrocarbons.In order to reach desirable assimilation effect, first order drip washing operating temperature preferably is controlled at 5～50 ℃, select stainless steel, plastics or porcelain corrosion-resistant filling for use, the filler type can be Raschig ring, Pall ring, cascade ring, rectangular saddle ring etc., the optional 20～50mm of filler nominal diameter.Packed tower structure and operation determine that by the conventional knowledge in this area be generally 2～5m as bed stuffing height, empty tower gas velocity is generally 0.4～2.0m/s, and liquid-gas ratio is generally 5～20L/m
3Leacheate pH value during cycling elution is reduced to and need be changed or replenish fresh minute lime set at 7.5～9.0 o'clock.In the sour water stripping process downtime or before running well, can adopt external ammoniacal liquor or contain the ammoniacal liquor, its solution that contains other alkaline matter of other alkaline matter absorption liquid as first order drip washing.Acid sewage storage tank discharging gas can be the nature discharging, also can adopt air inducing equipment to draw.
In the inventive method, the discharging gas that first order drip washing purifies carries out second level drip washing and purifies, and leacheate can adopt the stripping that produces in the stripping process to purify waste water, and also can adopt water for industrial use.Owing to adopt certain density ammonia spirit,, adopt discharging water purification or water for industrial use ammonia wherein effectively can be absorbed in the first order drip washing purification process so have a spot of ammonia in the discharging gas.Method of operating, equipment and operating condition that second level drip washing purifies can be selected in above-mentioned first order drip washing opereating specification.Drip washing relief liquor in the second level can enter and go stripping to handle in the acid sewage storage tank again.
In the inventive method, first order drip washing and second level drip washing can be operated in two independent device, also two-stage drip washing can be attached in the device to divide two sections and carry out, and reduce device quantity.
The inventive method combines sour water stripping process and acid sewage storage tank discharging gas decontamination process, can reach desirable purified treatment effect.And acid sewage storage tank discharging gas purifying treatment method of the present invention can not need external any material, and the two-stage absorbent all can be from the sour water stripping process.Leacheate after the washing does not need newly to establish other processing procedure, still can handle in the sour water stripping process, realizes closed-circuit operation, does not exert an influence to external world.The inventive method equipment is simple, and operating cost is low, does not have potential safety hazard.
Description of drawings
Fig. 1 is a kind of typical process schematic diagram of sour water stripping process of the present invention and acid sewage storage tank discharging gas purification process technique combined process, wherein the sour water stripping process adopts single tower stripping process, and side line is extracted rich ammonia vapour fractional condensation process out and adopted three grades of fractional condensation technologies.
The specific embodiment
Further specify the technical process that the present invention relates to below in conjunction with accompanying drawing.
As shown in Figure 1, sour water 1 is pooled to and carries out buffer storage in the acid sewage storage tank 2, enter stripper 4 by pipeline 3 then, the stripper top obtains being rich in hydrogen sulfide sour gas 5 and enters other device and further handle, and the stripper bottom obtains stripping and purifies waste water and 6 can be used as the fresh water (FW) reuse or enter the sewage-farm and handle.Stripper 4 middle part side lines 7 are extracted the gas phase mixture of ammonia and water out, carry out first order fractional condensation, fractional condensation gas phase 8 enters second level fractional condensation, and second level fractional condensation gas phase 9 enters third level fractional condensation, third level fractional condensation gas phase 10 is the very high ammonia of purity, and further refining usually and liquefaction is commercial liquefied ammonia.First order branch lime set 11, second level branch lime set 12, the third level divide the lime set 13 can be separately or mix the leacheate that purifies elution device 14 as the first order of acid water storage tank 2 discharging gas 15, and leacheate is discharged in the acid water storage tank 2 after absorbing in the discharging gas odorant pollutant such as hydrogen sulfide.The discharging gas that purifies through first order drip washing carries out second level elution device 16, stripping at the bottom of the employing stripping Tata is purified waste water or other qualified discharge waste water is leacheate, drip washing absorbs odor pollution materials such as ammonia wherein, discharging gas 17 after second level drip washing purifies has been eliminated odorant pollutant, absorption liquid enters acid water storage tank 2 and further handles, whole foul gas processing procedure does not have pollutant emission, realizes closed cycle.
Further specify the method for operating and the effect of the inventive method below by embodiment.In conjunction with existing sour water list tower stripping process, on the basis of the single tower stripping process of certain enterprise, use its side line branch lime set and stripping to purify waste water and be leacheate, carry out the present invention's experiment, single tower stripping process adopts the existing method of operating in this area, repeats no more among the application.
Certain enterprise's acid water storage tank distributes the about 1000m of tolerance
3/ h, main odorant pollutant is formed as shown in table 1.The stripper side line is extracted out and to be condensed into 3 grades of condensations, and wherein the weight concentration of the fractional condensation liquefied ammonia of third level condensation is about 30%, the stripping middle concentration of hydrogen sulfide 5～15mg/L that purifies waste water, ammonia concentration 20～50mg/L.With above-mentioned two kinds of absorption liquids that liquid is acid water storage tank discharging gas purified treatment.
The main odor pollution substrate concentration of table 1 acid water storage tank discharging gas
| Main malodorant kind | Malodorant kind concentration (mg/m 3) |
| Hydrogen sulfide | 100～12000 |
| |
10～2000 |
| Ammonia | 50～10000 |
| Volatile organic matter (VOC) | 500～1000 |
Acid sewage storage tank adopts two-stage drip washing purification run.Eluting column adopts packed tower, and filler is Dg50 plastics Pall rings.First order eluting column diameter 600mm, filler floor height 3000mm, leacheate is from three grades of fractional condensation systems of acid water stripping ammonia, ammonia weight concentration 30%, liquid-gas ratio 6～8L/m
3Second level eluting column diameter 700mm, filler floor height 4000mm, leacheate are that stripping is purified waste water, liquid-gas ratio 12～15L/m
3First order drip washing and second level drip washing operating temperature are controlled at 40 ℃～50 ℃.The leacheate of first order packed tower recycles in tower, replenishes new branch lime set when leacheate pH value reduces to 8.5.The leacheate of second level packed tower does not carry out cycling.The relief liquor of first order drip washing and second level drip washing all enters the acid water storage tank.Table 2 is the purified treatment effects at the acid sewage storage tank discharging gas of different time monitoring.
The purified treatment condition and the clean-up effect of table 2 acid sewage storage tank discharging gas
According to embodiment 1 described method, wherein filler adopts Dg38 stainless steel rectangular saddle ring.First order eluting column diameter 600mm, filler floor height 2600mm, leacheate is from acid water stripping ammonia fractional condensation system, and for secondary divides the mixed solution of lime set and three fraction lime sets, the weight concentration of ammonia is 20%, liquid-gas ratio 6～8L/m
3Second level eluting column diameter 700mm, filler floor height 3500mm, leacheate are that stripping is purified waste water, liquid-gas ratio 12～15L/m
3First order drip washing and second level drip washing operating temperature are controlled at 35 ℃～45 ℃.The leacheate of first order packed tower recycles in tower, replenishes new branch lime set when leacheate pH value reduces to 9.The leacheate of second level packed tower does not carry out cycling.The relief liquor of first order drip washing and second level drip washing all enters the acid water storage tank.Table 3 is the purified treatment effects at the acid sewage storage tank discharging gas of different time monitoring.
The purified treatment condition and the clean-up effect of table 3 acid sewage storage tank discharging gas
Claims (10)
1. the purifying treatment method of an acid sewage storage tank discharging gas, on the basis of existing sour water stripping process, acid sewage storage tank discharging gas purifies through two-stage drip washing, storage tank discharging gas at first purifies through first order drip washing, leacheate adopts the branch lime set of extracting ammonia fractional condensation process in the sour water stripping process out, the discharging gas that purifies through first order drip washing carries out second level drip washing purification, and leacheate is purifying waste water or water for industrial use of producing in the sour water stripping process.
2. in accordance with the method for claim 1, it is characterized in that described sour water stripping process is the double tower stripping process, or single tower stripping process.
3. according to claim 1 or 2 described methods, it is characterized in that in the described sour water stripping process that the fractional condensation process that stripper is extracted rich ammonia gas out adopts 2 grades or 3 grades.
4. in accordance with the method for claim 1, it is characterized in that described sour water is from hydrogenation plant, atmospheric and vacuum distillation unit, coking plant and the catalytic cracking unit of petroleum refining, PETROLEUM PROCESSING enterprise one or more.
5. in accordance with the method for claim 1, it is characterized in that arbitrary fraction lime set of fractional condensation process in the described first order drip washing employing stripping process, perhaps what divides lime set to mix use.
6. in accordance with the method for claim 3, adopting 2 grades of fractional condensation if it is characterized in that described stripping process, is leacheate with second level branch lime set; If stripping process adopts 3 grades of fractional condensation, be leacheate with the second level and/or third level branch lime set.
7. in accordance with the method for claim 1, the leacheate that it is characterized in that described first order drip washing once passes through packed tower, perhaps all or part of recycling is reduced to minute lime set of replenishing continuously or off and in the stripping process at 7.5～9.0 o'clock in leacheate pH value when recycling; The leacheate of discharging enters acid sewage storage tank, perhaps enters stripper.
8. in accordance with the method for claim 1, it is characterized in that described first order drip washing operating temperature is controlled at 5～50 ℃, selects stainless steel, plastics or porcelain corrosion-resistant filling for use.
9. in accordance with the method for claim 1, it is characterized in that described acid sewage storage tank discharging gas is the nature discharging, perhaps adopts air inducing equipment to draw.
10. in accordance with the method for claim 1, it is characterized in that described first order drip washing and second level drip washing operates in two independent device, perhaps two-stage drip washing is attached to and divides two sections in the device and carry out.
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| CN2007100103737A CN101239271B (en) | 2007-02-09 | 2007-02-09 | Cleaning treatment method of acid sewage storage tank discharging gas |
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|---|---|---|---|
| CN2007100103737A CN101239271B (en) | 2007-02-09 | 2007-02-09 | Cleaning treatment method of acid sewage storage tank discharging gas |
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| CN101239271A true CN101239271A (en) | 2008-08-13 |
| CN101239271B CN101239271B (en) | 2010-09-15 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898071B (en) * | 2009-05-25 | 2012-09-12 | 中国石油化工股份有限公司 | Method for treating sulfur- and hydrocarbon-containing foul waste gas |
| CN102781843A (en) * | 2009-12-16 | 2012-11-14 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| CN102908882A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Treatment method for emissions of sour water storage tank |
| CN107639090A (en) * | 2016-12-01 | 2018-01-30 | 中国石油化工股份有限公司 | Acid water storage tank shut-down (breakdown) mainteance sulphur iron rot product incidents of spontaneous combustion prevention method |
| CN107827248A (en) * | 2017-11-30 | 2018-03-23 | 沈阳石蜡化工有限公司 | Sewage disposal system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091140C (en) * | 2000-08-03 | 2002-09-18 | 中国石油化工股份有限公司 | Ammonia water process to desulfurize liquefied gas |
| CN1283346C (en) * | 2003-09-17 | 2006-11-08 | 镇江市江南环保设备研究所 | Fuel coal smoke low oxidation rate desulfur method |
-
2007
- 2007-02-09 CN CN2007100103737A patent/CN101239271B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898071B (en) * | 2009-05-25 | 2012-09-12 | 中国石油化工股份有限公司 | Method for treating sulfur- and hydrocarbon-containing foul waste gas |
| CN102781843A (en) * | 2009-12-16 | 2012-11-14 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| CN102781843B (en) * | 2009-12-16 | 2014-06-18 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| CN102908882A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Treatment method for emissions of sour water storage tank |
| CN102908882B (en) * | 2011-08-01 | 2015-06-17 | 中国石油化工股份有限公司 | Treatment method for emissions of sour water storage tank |
| CN107639090A (en) * | 2016-12-01 | 2018-01-30 | 中国石油化工股份有限公司 | Acid water storage tank shut-down (breakdown) mainteance sulphur iron rot product incidents of spontaneous combustion prevention method |
| CN107827248A (en) * | 2017-11-30 | 2018-03-23 | 沈阳石蜡化工有限公司 | Sewage disposal system |
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| CN101239271B (en) | 2010-09-15 |
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