CN104071884A - Vacuum potassium carbonate desulfurizing solution post processing method - Google Patents
Vacuum potassium carbonate desulfurizing solution post processing method Download PDFInfo
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- CN104071884A CN104071884A CN201310108477.7A CN201310108477A CN104071884A CN 104071884 A CN104071884 A CN 104071884A CN 201310108477 A CN201310108477 A CN 201310108477A CN 104071884 A CN104071884 A CN 104071884A
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- solution
- potassium carbonate
- doctor solution
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Abstract
The invention discloses a vacuum potassium carbonate desulfurizing solution post processing method which comprises the following steps: 1, injecting a desulfurizing solution into a reaction tank, and adding hydrogen peroxide and ferrous sulfate; 2, stirring for reaction, and collecting a reaction gas; 3, sedimentating a reaction solution for solid-liquid separation, and respectively treating separated solution and solid; 4, regulating the pH value of the separated solution, and collecting the reaction gas; and 5, carrying out biochemical coagulating sedimentation on separated sediments. By adopting the technical scheme, as for the vacuum potassium carbonate desulfurizing solution post processing method disclosed by the invention, a desulfurizing solution post processing method is added on the basis of a coke oven gas vacuum carbonate process, the solution outwards discharged from a desulfurizing solution system can be treated by utilizing a desulfurizing solution pretreatment device and the KCN and KSCN which are contained in the outwards discharged desulfurizing solution can be effectively removed, the KCN and KSCN which are contained in the outwards discharged desulfurizing solution are less than 10 g/L, the problem of influence of the outwards discharged desulfurizing solution on a biochemical wastewater treatment system can be solved and the normal operation of a biochemical device is ensured.
Description
Technical field
The present invention relates to coke oven gas purification method, more particularly, relate to a kind of vacuum potassium carbonate doctor solution post-treating method.
Background technology
In process of coking, in feed coal, approximately 30%～35% sulphur changes into H
2s sulfides, with NH
3form the impurity in coal gas, wherein H together with HCN etc.
2the mass concentration of S is generally 5～8g/m
3, the mass concentration of HCN is 1～2.5g/m
3.H
2s and HCN have very strong corrodibility, toxicity, H in air
2when being 0.1%, the volume fraction of S just can make people fatal.When coke-oven gas is used as fuel, H
2s and products of combustion SO thereof
2all poisonous, meeting serious environment pollution, so coal gas must carry out desulfuration and decyanation before using as fuel, is purified coal gas.
Various gas purification methods in the wet-type oxidation technology of current extensive employing and wet absorption technique, the amount that produces coking chemical waste water is large, complicated component, and the water yield and water quality unstable, this has just increased the difficulty of wastewater treatment.To the processing of coking chemical waste water, extensively adopt common biochemical processing process, though it phenol, cyanogen etc. in waste water can be removed effectively, to NH a large amount of in waste water
3-N does not almost have Degradation.
For head it off, except renovating traditional coking waste water treatment process, also should be devoted to research and develop the novel purification process that can significantly reduce wastewater discharge.It is existing a kind of novel flue gas purifying technique---flue gas condensing purification process is applied to coke oven gas purification system, main thought is by using cooling and dedusting (dry quenching(of coke)) stage by stage to substitute the directly wet quenching with ammonia spray coke-oven gas in traditional coking system, like this, not only can recycle a large amount of coke sensible heats, and can greatly reduce wastewater discharge, can carry out the H in separation and purification coke-oven gas by deep condensation simultaneously
2the impurity such as S, HCN.
Almost do not have for the relevant report of vacuum potassium carbonate doctor solution processing at present, more for the report of HPF method doctor solution treatment process, mainly comprise:
1. source is controlled: by the optimization of operation index, reduce the generation of secondary salt as far as possible, thereby reduce the discharge of waste liquid,
2. coal blending processing: desulfurization waste liquor is assigned in coking coal and is processed, each ammonium salts thermo-cracking in coke oven, most of salt is finally decomposed into NH
3, H
2s, CO
2and N
2.
3. combustion method: desulfurization waste liquor is delivered to combustion unit and burn, generate sulfurous gas, then send to relieving haperacidity workshop section extracting sulfuric acid.
4. Crystallization Separation: adopt the method for evaporation that secondary salt is separated from desulfurization waste liquor with the form of crystallization.
Summary of the invention
Object of the present invention aims to provide a kind of vacuum potassium carbonate doctor solution post-treating method, solves in prior art prussiate in doctor solution, problem that thiocyanide content is high.
According to the present invention, a kind of vacuum potassium carbonate doctor solution post-treating method is provided, comprise the following steps: step 1, doctor solution is injected to reactive tank, and add hydrogen peroxide and ferrous sulfate.Step 2, stirring reaction.Step 3, by reaction solution precipitation, solid-liquid separation, and process respectively solid and the solution after separating.
According to one embodiment of the invention, also comprise: step 4, adjust the pH value that separates rear solution.Step 5, carries out biochemical coagulating sedimentation by the throw out after separating.
According to one embodiment of the invention, collect the reactant gases of step 2, step 3 and step 4, by reactant gases relieving haperacidity processing.
According to one embodiment of the invention, doctor solution comprises prussiate and thiocyanide.
According to one embodiment of the invention, prussiate comprises potassium cyanide, and content is 50g/L, and thiocyanide comprises potassium thiocyanate, and content is 75g/L.
According to one embodiment of the invention, the content of doctor solution is 500～750kg/h, and the content of hydrogen peroxide is 10～20kg/h, and the content of ferrous sulfate is 10～20kg/h.
According to one embodiment of the invention, the reaction times of step 2 is 3～3.5h.
According to one embodiment of the invention, utilize sodium hydroxide that the pH value of the solution of step 4 is adjusted to neutrality.
According to one embodiment of the invention, neutral solution is inputted to the processing of ammonia still emptying groove.
According to one embodiment of the invention, step 1 to the temperature of reaction of step 5 is normal temperature.
Adopt technical scheme of the present invention, on coke-oven gas vacuum carbonation technique basis, increase sulphur liquid post-treating method, utilize doctor solution pretreatment unit to process the row's of doctor solution system China and foreign countries solution, effective elimination is arranged KCN, the KSCN in doctor solution outward, make KCN, KSCN in outer row's doctor solution be less than 10g/L, effectively solve the impact of outer row's doctor solution on biochemical waste water treatment system, ensured the normal operation of biochemical device.
Brief description of the drawings
In the present invention, identical Reference numeral represents identical feature all the time, wherein:
Fig. 1 is vacuum potassium carbonate doctor solution post-treating method schema;
Fig. 2 is the setting drawing of vacuum potassium carbonate doctor solution post-treating method.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with drawings and Examples.
The present invention is mainly the emission problem in order to solve vacuum potassium carbonate doctor solution, because of the KCN in doctor solution, the components such as KSCN can suppress the microbial growth of biochemical waste water device and produce to poison, control and process if do not added, directly discharge is by the KCN causing in waste water, KSCN content is higher, thereby have influence on the normal operation of biochemical waste water treatment unit, a kind of aftertreatment technology of coke-oven gas vacuum carbonate doctor solution is provided for this reason, solve outer row's doctor solution KCN, KSCN produces the problem of poisoning to the microbial bacterial of biochemical waste water treatment unit, make the biochemical device can steady running.
Feature of the present invention is to adopt the principle of ferrous sulfate and hydrogen peroxide oxidation, coagulating sedimentation to process the SCN in doctor solution
-with CN
-, the waste liquid of handling well enters biochemical device processing together with distilled ammonia wastewater, without unnecessary product output.
Coke-oven gas vacuum potassium carbonate method sulfur removal technology is to adopt solution of potassium carbonate as sweetening agent, coke-oven gas carries out reverse contact with the lean solution (solution of potassium carbonate) of coming at the bottom of regenerator column, after absorbing the acidic components such as hydrogen sulfide in coal gas, prussic acid, carbonic acid gas, become rich solution, be sent to regenerator column, under vacuum condition, separate the sour gas such as sucking-off hydrogen sulfide, prussic acid, carbonic acid gas, after condensing cooling by vacuum pumping toward sulphuric acid plant.
Vacuum potassium carbonate technique belongs to chemical absorption method, removing H in coal gas
2when S, most of HCN and a small amount of CO
2also be absorbed, therefore belong to multicomponent chemical and absorb.Doctor solution alkali source is potassium hydroxide solution, with the CO in coal gas
2reaction participates in absorption reaction after generating salt of wormwood.
The reaction mainly occurring at thionizer is:
2KOH+CO
2→K
2CO
3
K
2CO
3+H
2S→KHCO
3+KHS
K
2CO
3+HCN→KHCO
3+KCN
K
2CO
3+CO
2+H
2O→2KHCO
3
The solution of potassium carbonate that has absorbed hydrogen sulfide, prussic acid etc. enters desorption tower top, with reverse contact of thermal vapor stream of rising at the bottom of tower.Under nearly vacuum condition (working pressure is at 15-18kpa), by stripping out, rich solution changes into lean solution to the sour gas in solution of potassium carbonate, and reaction as follows occurs:
KHCO
3+KHS→K
2CO
3+H
2S
KHCO
3+KCN→K
2CO
3+HCN
2KHS+2O
2→K
2S
2O
3+H
2O
2KCN+2H
2S+O
2→KCNS+2H
2O
Because side reaction is irreversible, the salt therefore generating is as K
2s
2o
3, the dependence such as KCNS heating stripping cannot decompose, these non-renewable salts run up to certain concentration in solution, the decline, viscosity increase, the alkaline consumption that cause solution receptivity are increased, so solution system is discharge section solution continuously, to control the concentration of non-renewable salt in solution.
The solution of discharging in system enters after ammonia steaming device ammonia still process, directly enters the processing of biochemical waste water treatment system.Because contain certain density prussiate, thiocyanide etc. in doctor solution, although quantity discharged is little, but KCN, KSCN content are high, wherein potassium cyanide content is about 50g/L left and right, KSCN content is about 75g/L left and right, this part pollutent is very big on the impact of subsequent wastewater treatment system, causes the operation of biochemical device extremely unstable.
Natural bacterial classification far can not adapt to the cyanide wastewater of every liter of several milligrams of concentration, even bacterial classification is tamed, it is progressively adapted to, and is also difficult to tolerate the prussiate of higher concentration.High density produces the effects such as murder by poisoning to follow-up stable biochemical treatment containing prussiate sewage discharge meeting; thereby cause the irregular operating of Sewage treatment systems; so need to increase doctor solution treatment unit; to reduce the content of KCN, KSCN in doctor solution, thereby reach the steady running of the follow-up biochemical treatment system of protection.
As shown in Figure 1, the invention provides a kind of vacuum potassium carbonate doctor solution post-treating method of corresponding the problems referred to above, it comprises 5 main steps:
S1: doctor solution is injected to reactive tank, and add hydrogen peroxide and ferrous sulfate.
S2: stirring reaction.
S3: by reaction solution precipitation, solid-liquid separation, and process respectively solid and the solution after separating.
S4: the pH value of adjusting solution after separating.
S5: the throw out after separating is carried out to biochemical coagulating sedimentation.
Carry out the device of above-mentioned steps as shown in Figure 2, describe above-mentioned 5 steps in detail below by Fig. 2.
Doctor solution of the present invention comprises prussiate and thiocyanide, and wherein prussiate is mainly potassium cyanide, and content is about 50g/L, and thiocyanide is mainly potassium thiocyanate, and content is about 75g/L.
Doctor solution in solution system is controlled to flow by under meter 2 to be delivered in main reactor 1 at 500～750kg/h, utilize hydrogen peroxide volume pump 3 and ferrous sulfate volume pump 4 to add hydrogen peroxide and ferrous sulfate in reactive tank 1 front portion, hydrogen peroxide is controlled at 10～20kg/h, and ferrous sulfate is controlled at 10～20kg/h.
After main reactor 1 use stirrer 11 fully stirs, reacts, reaction time is 3～3.5h, remove KCN, KSCN in solution, rear solution enters and in settling bath 12, carries out solid-liquid separation, top solution enters PH adjustment tank 13, add sodium hydroxide that the pH value of solution is adjusted to after neutrality with sodium hydroxide volume pump 15, enter ammonia still emptying groove 5 through U-shaped syphon trap 14.
Introduce sulphuric acid plant incinerator 6 from main reactor 1, settling bath 12, adjustment tank 13 sour gas out through supercharger.
Be evacuated to biochemical device coagulative precipitation tank 7 from settling bath 12 bottoms throw out out through pump, carry out carrying out again subsequent disposal after coagulating sedimentation.
The temperature of W-response is controlled at normal temperature.
Below by a series of experimental data, beneficial effect of the present invention is described.
Get 6 groups of samples, process respectively according to vacuum potassium carbonate doctor solution post-treating method of the present invention, the result obtaining is as shown in the table:
As can be seen from the above table, the present invention can reach more than 87.4% the average desulfurization degree of KCN, can reach more than 88.5% the average desulfurization degree of KSCN.
Those of ordinary skill in the art will be appreciated that, above specification sheets is only one or more embodiments in the numerous embodiment of the present invention, and not uses limitation of the invention.Any equalization variation, modification for the above embodiment and be equal to the technical schemes such as alternative, as long as connotation scope according to the invention, all will drop in the scope that claims of the present invention protect.
Claims (10)
1. a vacuum potassium carbonate doctor solution post-treating method, is characterized in that, comprises the following steps:
Step 1, injects reactive tank by doctor solution, and adds hydrogen peroxide and ferrous sulfate;
Step 2, stirring reaction;
Step 3, by reaction solution precipitation, solid-liquid separation, and process respectively solid and the solution after separating.
2. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 1, is characterized in that, further comprising the steps of:
Step 4, adjusts the pH value that separates rear solution;
Step 5, carries out biochemical coagulating sedimentation by the throw out after separating.
3. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 2, is characterized in that, collects the reactant gases of step 2, step 3 and step 4, by described reactant gases relieving haperacidity processing.
4. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 1, is characterized in that, described doctor solution comprises prussiate and thiocyanide.
5. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 4, is characterized in that, described prussiate comprises potassium cyanide, and content is 50g/L, and described thiocyanide comprises potassium thiocyanate, and content is 75g/L.
6. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 1, is characterized in that, the content of described doctor solution is 500～750kg/h, and the content of described hydrogen peroxide is 10～20kg/h, and the content of described ferrous sulfate is 10～20kg/h.
7. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 1, is characterized in that, the reaction times of described step 2 is 3～3.5h.
8. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 2, is characterized in that, utilizes sodium hydroxide that the pH value of the solution of described step 4 is adjusted to neutrality.
9. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 8, is characterized in that, by the processing of described neutral solution input ammonia still emptying groove.
10. vacuum potassium carbonate doctor solution post-treating method as claimed in claim 2, is characterized in that, described step 1 to the temperature of reaction of step 5 is normal temperature.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN118063032A (en) * | 2024-03-15 | 2024-05-24 | 威海天宇新材料科技有限公司 | Recycling treatment process for wastewater from rubber vulcanizing agent production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN118063032A (en) * | 2024-03-15 | 2024-05-24 | 威海天宇新材料科技有限公司 | Recycling treatment process for wastewater from rubber vulcanizing agent production |
| CN118063032B (en) * | 2024-03-15 | 2024-07-23 | 威海天宇新材料科技有限公司 | Recycling treatment process for wastewater from rubber vulcanizing agent production |
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Application publication date: 20141001 |