CN101979340A - Desulfuration waste liquid treatment process and equipment - Google Patents
Desulfuration waste liquid treatment process and equipment Download PDFInfo
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- CN101979340A CN101979340A CN2010105442895A CN201010544289A CN101979340A CN 101979340 A CN101979340 A CN 101979340A CN 2010105442895 A CN2010105442895 A CN 2010105442895A CN 201010544289 A CN201010544289 A CN 201010544289A CN 101979340 A CN101979340 A CN 101979340A
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- desulfurization waste
- waste liquid
- hydrolysis reactor
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Abstract
The invention relates to a desulfuration waste liquid treatment process, in particular to a desulfuration waste liquid treatment process and equipment thereof. The desulfuration waste liquid is treated by adopting a heating hydrolysis mode in the process, namely the desulfuration waste liquid is conveyed into a closed hydrolysis reactor, cyanide in the desulfuration waste liquid is hydrolyzed into non-toxic or low-toxic compounds such as formate, ammonia and the like at a certain temperature under a certain pressure, and the hydrolyzed products are directly conveyed to an ammonia still. The process has the advantages that: due to primary treatment of the desulfuration waste liquid before evaporating the ammonia, the cyanide content of the desulfuration waste liquid is effectively reduced, and the cyanide content of the ammonia evaporation wastewater after the desulfuration waste liquid is blended is close to the index before the desulfuration waste liquid is not blended; and the wastewater is discharged after biochemical secondary treatment so that the water quality meets the national discharge standard requirement.
Description
Technical field
The present invention relates to desulfurization waste liquor treatment process technical field, particularly a kind of desulfurization waste liquor treatment process and equipment thereof.
Background technology
Vacuum salt of wormwood method sulfur removal technology is a kind of Technology of coke oven gas desulfurization efficiently.Compare with other sulfur method, have advantages such as energy-conservation, desulfuration and decyanation efficient height, flow process is simple, operation is reliable, facility investment is lower, thereby obtained widespread use at coking industry.
Vacuum salt of wormwood method coal gas desulfurization technology belongs to the absorption process desulfurization, can produce a small amount of waste liquid in technological process, and its main component has K
2CO
3, KHCO
3, KHS, KCN, KCNS, K
2S
2O
3, K
4[Fe (CN)
6], HCN etc.As everyone knows, prussiate belongs to highly toxic substance, and therefore serious threat environment and Biosafety must externally be got rid of the sulphur waste liquid and be handled, and reduce total cyanogen content, to meet national relevant emission standards.
Present stage mainly adopts dual mode to handle vacuum carbonate desulfurization waste liquor at coking industry: the first, waste liquid is blended in the remained ammonia, and after ammonia still process, be sent to biochemical further processing with waste water.The second, the reduction heat solution; This dual mode remains in defective at aspects such as reliability of operation, working cost and investments, is described as follows:
First kind of mode of a: ammonia still process adds biochemistry, is waste liquid is blended in the remained ammonia, is sent to biochemical further processing with waste water after ammonia still process.Practice shows: the ammonia-nitrogen content behind the ammonia still in the waste water changes not quite before sneaking into than desulfurization waste liquor, but the CN in the waste water after the ammonia still process
-Concentration significantly improves before sneaking into than desulfurization waste liquor.Because the CN of waste water middle and high concentration
-Pollutent is to the restraining effect of biological bacterium and difficulty is degraded, and causes the waste water after the biochemical treatment to be difficult to up to standard; Though or up to standard reluctantly, the biological bacterium in the activated sludge is often dead, has influenced biochemical stable operation.For this reason, though can adopt the way of handling in biochemistry inlet dosing etc., increased the biochemical treatment cost.This shows, directly utilize ammonia still process to add the biochemical method one-level and handle desulfurization waste liquor, have difficulty.
The b second way: the reduction heat solution is that desulfurization waste liquor is sent into the reduction decomposition stove, burns in 800～850 ℃ reducing atmosphere, and the inertia salt is decomposed, and reclaims alkali and return desulphurization system.This method facility investment height, and a large amount of coke-oven gas (the main component H of consumption that needs in service
2) as reducing gas, the processing cost height, complicated operation is so far in China's precedent of also not going into operation.
In sum, for guaranteeing that distilled ammonia wastewater contains cyanogen and satisfies the water inlet index request that wastewater biochemical is handled, at present vacuum carbonate coal gas desulfurization waste liquid is still lacked comparatively perfect treatment process and equipment.
Summary of the invention
The purpose of this invention is to provide a kind of desulfurization waste liquor treatment process and equipment, before ammonia still process desulfurization waste liquor being carried out one-level handles, effectively reduce the desulfurization waste liquor cyanide content, make the distilled ammonia wastewater that is blended into behind the desulfurization waste liquor contain cyanogen near the index that is not blended into before the desulfurization waste liquor; Waste water discharges after biochemical second-stage treatment again, makes water quality satisfy the discharging standards requirement.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of desulfurization waste liquor treatment process, the mode of this process using heating hydrolysis is handled desulfurization waste liquor, desulfurization waste liquor is sent in the airtight hydrolysis reactor, made it under certain temperature and pressure condition, make prussiate in the desulfurization waste liquor be hydrolyzed into the compound of nontoxic or little poison such as formate, ammonia.
Described hydrolysising reacting temperature is 110 ℃～230 ℃.
Described hydrolysis reaction pressure is 3～10MPa.
Described hydrolysis time is 10～80min.
The basicity PH of described desulfurization waste liquor 〉=8.5.
The hydrolysis after product directly is sent to ammonia still or biochemistry carries out second-stage treatment.
Realize the equipment of described desulfurization waste liquor treatment process, comprise waste water storage tank, feedstock pump, hydrolysis reactor, waste water storage tank is connected with hydrolysis reactor by connecting tube, be provided with feedstock pump on the connecting tube of waste water storage tank and hydrolysis reactor, hydrolysis reactor connects ammonia steaming device by the material discharge line.
Be provided with temperature transmitter in the described hydrolysis reactor, temperature transmitter passes to thermoswitch with temperature signal, thermoswitch dominant discharge control valve opening.
Be provided with pressure warning unit in the described hydrolysis reactor.
Be provided with the level display and alarm device in the described hydrolysis reactor.
Compare with existing vacuum salt of wormwood method desulfurization waste liquor treatment process, the present invention has flow process weak point, easy handling, it is applied widely that waste water is contained cyanogen concentration, reaction thoroughly, prussiate clearance height, remarkable advantages such as non-secondary pollution; Significant to the vacuum salt of wormwood sulfur removal technology, the protection environment that improve coking industry.Details are as follows for beneficial effect:
1) technical process is short, easy handling;
The present invention directly sends into vacuum salt of wormwood method coal gas desulfurization waste liquid in the airtight hydrolysis reactor, generally speaking, desulfurization waste liquor self pH value can satisfy the requirement of hydrolysis material basicity, do not need artificial adjusting, desulfurization waste liquor is heated the pressurization automatically that heats up, the assurance certain reaction can be decomposed after the time, did not consume other chemical agents.Technical process is short, easy handling.
2) it is applied widely waste water to be contained cyanogen concentration;
The present invention contains to waste water that cyanogen concentration is applied widely, elasticity is big, the hydrolysis that can adapt to high cyanide containing wastewater removes the cyanogen requirement, concentration there is good decomposition effect at 30g/l with interior KCN, KCNS, can satisfies difference and contain the desulfurization waste liquor hydrolysis of cyanogen concentration except that the cyanogen requirement.
3) thorough, the prussiate clearance height of reaction, non-secondary pollution;
The present invention has the advantage that can handle free state and complex state prussiate, reaction thoroughly, the prussiate clearance is more than 90%, and the prussiate in the desulfurization waste liquor is decomposed into the compound of nontoxic or little poison such as formate, ammonia, and the hydrolysis after product directly is sent to ammonia still, do not efflux non-secondary pollution.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Among the figure: 1-waste water storage tank 2-feedstock pump 3-hydrolysis reactor 4-pressure regulator valve 5-flow control valve
PI-pressure warning unit LIA-level display and alarm device TI-temperature transmitter FIC-thermoswitch PIC-pressure-regulator
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
See Fig. 1, a kind of technology that is used for vacuum salt of wormwood method coal gas desulfurization liquid waste disposal, the mode of this process using heating hydrolysis is handled desulfurization waste liquor, desulfurization waste liquor is sent in the airtight hydrolysis reactor 3, make it under certain temperature and pressure condition, make prussiate in the desulfurization waste liquor be hydrolyzed into the compound of nontoxic or little poison such as formate, ammonia, the hydrolysis after product directly is sent to ammonia still.Hydrolysising reacting temperature is 110 ℃～230 ℃; Hydrolysis reaction pressure is 3～10MPa; Hydrolysis time is 10～80min; The basicity PH of desulfurization waste liquor 〉=8.5.
In hydrolysis reactor 3, the chemical equation of desulfurization waste liquor is as follows:
KCN+2H
2O＝NH
3+HCOOK
HCOOK+KOH＝K
2CO
3+H
2
2KCNS+5H
2O＝K
2CO
3+CO
2+2H
2S+2NH
3
In the said hydrolyzed reaction, KCN and KCNS finally resolve into salt of wormwood and ammonia.
Realize the equipment of vacuum salt of wormwood method coal gas desulfurization process for treating waste liquor, comprise waste water storage tank 1, feedstock pump 2, hydrolysis reactor 3, waste water storage tank 1 is connected with hydrolysis reactor 3 by connecting tube, be provided with feedstock pump 2 on the connecting tube of waste water storage tank 1 and hydrolysis reactor 3, hydrolysis reactor 3 connects ammonia steaming device by the material discharge line.Be provided with temperature transmitter TI in the hydrolysis reactor 3, temperature transmitter TI passes to thermoswitch FIC with temperature signal, the aperture of thermoswitch FIC dominant discharge variable valve 5, and then the temperature in the control hydrolysis reactor.
Be provided with pressure warning unit PI in the hydrolysis reactor 3, be used for measuring the pressure in the hydrolysis reactor.Also be provided with level display and alarm device LIA in the hydrolysis reactor 3, be used for showing liquid level.The material discharge line that hydrolysis reactor 3 is connected with ammonia steaming device is provided with pressure regulator valve 4, and pressure regulator valve 4 is connected with pressure-regulator PIC.
The desulfurization waste liquor that is come by vacuum salt of wormwood desulfurizer enters waste water storage tank 1, sends into hydrolysis reactor 3 by feedstock pump 2.Be provided with temperature transmitter TI in the hydrolysis reactor 3, the temperature signal in thermoswitch FIC sends hydrolysis reactor 3.Thermoswitch FIC is according to the temperature of reaction of setting, and control heating-medium flow adjustable valve makes the temperature (110～230 ℃) that keeps regulation in the hydrolysis reactor 3.
Reach in the hydrolysis reactor 3 (110～230 ℃) after the temperature that is suitable for the desulfurization waste liquor hydrolysis, keep certain reaction after the time (10～80min), by pressure regulator valve 4 hydrolysate is sent into ammonia steaming device and continues to handle.
The present invention has the advantage that can process free state and complex state cyanide, reaction thoroughly, the cyanide clearance is more than 90%, and the cyanide in the desulfurization waste liquor is decomposed into the compound of nontoxic or little poison such as formates, ammonia, and the hydrolysis afterproduct directly is sent to ammonia still, do not efflux non-secondary pollution.
Claims (10)
1. desulfurization waste liquor treatment process, it is characterized in that, the mode of this process using heating hydrolysis is handled desulfurization waste liquor, desulfurization waste liquor is sent in the airtight hydrolysis reactor, make it under certain temperature and pressure condition, make prussiate in the desulfurization waste liquor be hydrolyzed into the compound of nontoxic or little poison such as formate, ammonia.
2. a kind of desulfurization waste liquor treatment process according to claim 1 is characterized in that, described hydrolysising reacting temperature is 110 ℃～230 ℃.
3. a kind of desulfurization waste liquor treatment process according to claim 1 and 2 is characterized in that described hydrolysis reaction pressure is 3～10MPa.
4. a kind of desulfurization waste liquor treatment process according to claim 1 and 2 is characterized in that described hydrolysis time is 10～80min.
5. a kind of desulfurization waste liquor treatment process according to claim 1 and 2 is characterized in that the basicity PH of described desulfurization waste liquor 〉=8.5.
6. a kind of desulfurization waste liquor treatment process according to claim 1 and 2 is characterized in that the hydrolysis after product directly is sent to ammonia still or biochemistry carries out second-stage treatment.
7. realize the equipment of claim 1 or 2 described desulfurization waste liquor treatment process, it is characterized in that, comprise waste water storage tank, feedstock pump, hydrolysis reactor, waste water storage tank is connected with hydrolysis reactor by connecting tube, be provided with feedstock pump on the connecting tube of waste water storage tank and hydrolysis reactor, hydrolysis reactor connects ammonia steaming device by the material discharge line.
8. desulfurization waste liquor treatment facility according to claim 7 is characterized in that, is provided with temperature transmitter in the described hydrolysis reactor, and temperature transmitter passes to thermoswitch with temperature signal, thermoswitch dominant discharge control valve opening.
9. desulfurization waste liquor treatment facility according to claim 7 is characterized in that, is provided with pressure warning unit in the described hydrolysis reactor.
10. desulfurization waste liquor treatment facility according to claim 7 is characterized in that, is provided with the level display and alarm device in the described hydrolysis reactor.
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| CN2010105442895A CN101979340A (en) | 2010-11-15 | 2010-11-15 | Desulfuration waste liquid treatment process and equipment |
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| CN2010105442895A CN101979340A (en) | 2010-11-15 | 2010-11-15 | Desulfuration waste liquid treatment process and equipment |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663805A (en) * | 2013-12-13 | 2014-03-26 | 武汉钢铁(集团)公司 | Method and device for pretreating coal gas desulfurization waste liquid through vacuum potassium carbonate method |
| CN104195349A (en) * | 2014-08-28 | 2014-12-10 | 福建省双旗山矿业有限责任公司 | Degradation treatment process for waste residues of cyanide tailings |
| CN104944556A (en) * | 2015-05-28 | 2015-09-30 | 中冶焦耐工程技术有限公司 | Hydrolysis reactor |
| CN105417813A (en) * | 2015-11-09 | 2016-03-23 | 宁波科新化工工程技术有限公司 | Technique for treating desulfurization waste solution of carbonate under vacuum |
| CN106927593A (en) * | 2015-12-29 | 2017-07-07 | 上海宝钢化工有限公司 | Vacuum potassium carbonate desulfurization waste liquor pretreatment unit |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857326A (en) * | 2010-07-05 | 2010-10-13 | 天津天达联合工程技术有限公司 | Comprehensive treatment method of high-concentration cyanogens-containing and thiocyanate-containing waste liquid |
-
2010
- 2010-11-15 CN CN2010105442895A patent/CN101979340A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857326A (en) * | 2010-07-05 | 2010-10-13 | 天津天达联合工程技术有限公司 | Comprehensive treatment method of high-concentration cyanogens-containing and thiocyanate-containing waste liquid |
Non-Patent Citations (2)
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| 《环境科学与技术》 200812 姜莉莉 加压水解法处理含氰废水的研究 141-,143 1-10 第31卷, 第12期 2 * |
| 《金属矿山》 200203 仲崇波 氰化物水解除氰的研究 22-25,28 1-10 第2002年卷, 第3期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663805A (en) * | 2013-12-13 | 2014-03-26 | 武汉钢铁(集团)公司 | Method and device for pretreating coal gas desulfurization waste liquid through vacuum potassium carbonate method |
| CN103663805B (en) * | 2013-12-13 | 2015-08-19 | 武汉钢铁(集团)公司 | A kind of pretreatment process of vacuum potassium carbonate method coal gas desulfurization waste liquid and device |
| CN104195349A (en) * | 2014-08-28 | 2014-12-10 | 福建省双旗山矿业有限责任公司 | Degradation treatment process for waste residues of cyanide tailings |
| CN104195349B (en) * | 2014-08-28 | 2016-09-14 | 福建省双旗山矿业有限责任公司 | A kind of cyanidation tailings waste residue degradation treatment technique |
| CN104944556A (en) * | 2015-05-28 | 2015-09-30 | 中冶焦耐工程技术有限公司 | Hydrolysis reactor |
| CN105417813A (en) * | 2015-11-09 | 2016-03-23 | 宁波科新化工工程技术有限公司 | Technique for treating desulfurization waste solution of carbonate under vacuum |
| CN105417813B (en) * | 2015-11-09 | 2018-01-26 | 宁波科新化工工程技术有限公司 | A kind of vacuum carbonate desulfuration waste liquid treatment process method |
| CN106927593A (en) * | 2015-12-29 | 2017-07-07 | 上海宝钢化工有限公司 | Vacuum potassium carbonate desulfurization waste liquor pretreatment unit |
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Application publication date: 20110223 |