CN106082535A - The processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid - Google Patents
The processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/20—Thiocyanic acid; Salts thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
Abstract
The processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid, described method is to add activated carbon in ammonia process of desulfurization waste liquid to decolour, decolouring filtering residue coal-blending coking, decolouring waste liquid adds reactor with sulphuric acid, add oxidant stirring, by evaporation drying, it is thus achieved that pretreatment salt-mixture, and carry out repeatedly extracting to pretreatment salt-mixture with liquid sulfur dioxide, it is thus achieved that ammonium thiocyanate solid and SO2Gas, SO2Gas reuses.This method utilizes liquid sulfur dioxide to extract the ammonium thiocyanate in mixed inorganic, extracts process simple, and efficiency high energy consumption is low.
Description
Technical field
The present invention relates to a kind of ammonia process of desulfurization method for treating waste liquid, say further, be a kind of to coke-oven plant's employing ammonia process
The method that during wet oxidation removing hydrogen sulfide, produced desulfurization waste liquor carries out recycling treatment.
Background technology
To the H in coke-stove gas2S and HCN gas removal, the general Wet-type oxidation sweetening method that uses, wherein HPF method is to utilize
Ammonia in coke-stove gas, as absorbent, carries out desulfuration and decyanation with HPF for catalyst, in sweetening process, along with side reaction
Generation can produce NH4SCN, (NH4)2S2O3Deng secondary salt, NH in desulfurization waste liquor4SCN, (NH4)2S2O3Content summation is more than 250g/L
Time, affect the activity of desulphurization catalyst, make desulphurization reaction speed reduce, have a strong impact on desulfuration efficiency, for ensureing the de-of desulfurizing agent
Sulphur efficiency, needs periodically to supplement fresh doctor solution without secondary salt to desulfurizer, and the desulfurization of exclusive segment high concentration secondary salt simultaneously is given up
Liquid, if this part waste liquid serious environment pollution of row's meeting outward, can not directly process by biochemical method again.
In the prior art, major part coke-oven plant desulfurization waste liquor is sprayed on coking coal with coking coal return coke oven high temperature divide
Solving, but this method increase the moisture in mixed coal, severe corrosion equipment, and pollute environment, winter, intractability was big.This
Outward, Some Enterprises uses salt extraction method, utilizes the difference of salt solubility, fractional crystallization, extracts rhodanate and thiosulfate etc.
Secondary salt.
Existing Publication No. CN103395805A discloses one and " prepares high-quality sulfur with coke-oven-gas desulfurization and decyanation waste liquid
The method of Sodium cyanate (NaOCN) ", the method adds auxiliary agent and removes the sodium thiosulfate in waste liquid, isolates inorganic salt impurities, then through decolouring,
Condensing crystallizing obtains sodium rhodanate.Sodium rhodanate is isolated from waste liquid by the method, and concentrated mother liquor recycles, and in waste liquid
Other inorganic salt fail to be obtained by.
Existing Publication No. CN 101219340A discloses the " process of a kind of discharged doctor solution of HPF desulfurization system of coke-oven plant
Technique ", this method uses catalysis oxidation-complex reaction, by adding CuSO4·5H2O and SCN in doctor solution-Generate intermediate
CuSCN complex, then uses alkaline process that CuSCN is converted into NaSCN or KSCN, and after process, doctor solution directly returns desulphurization system
Or deliver to biochemical system through ammonia still process process.This method is by SCN-Separate from doctor solution, S2O3 2-And SO3 2-It is oxidized to SO4 2-, but residue
Desulfurization waste liquor still has the SO of high concentration4 2-、S2O3 2-And SO3 2-Fail effectively to process, Cu in the most added chelating agent2+Also fail to
Completely reclaim thus produce secondary pollution.
Existing Publication No. CN 101597073A discloses that " a kind of coke gas desulfurization waste liquor prepares the side of ammonium thiocyanate
Method ", this method thiocyanate radical in calcium phosphate+ forage desulfurization waste liquor, then use sodium hydroxide solution back extraction, condensing crystallizing,
Washing is dried and prepares sodium rhodanate crystal.This method needs repeatedly to extract during preparing ammonium thiocyanate, back extraction, operation complexity,
And other components in untreated desulfurization waste liquor, utilization rate is low.
Existing Publication No. CN 101850952A discloses one and " extracts Ammonium hyposulfite. and Hydrogen thiocyanate in desulfurization waste liquor
The production technology of ammonium ", the method by settle, decolour, distillation of reducing pressure obtains Ammonium hyposulfite. solid, with organic solvent dissolving,
Backflow, heat filtering.Filter cake dries to obtain Ammonium hyposulfite., and filtrate obtains ammonium thiocyanate through decompression distillation, crystallization filtering drying.This method palpus
Through three decompression distillations, once refluxing, three crystallizations are filtered, and once dissolve, and process is complicated, and the required energy consumption of decompression distillation
Greatly, exist during organic solvent used uses and be lost and poisonous.
Existing Publication No. CN 101306885B discloses " recycling processing method of a kind of coking sulfur-containing waste water ", should
Method carries out resource recovery by the way of microfiltration or ultrafilter membrane, NF membrane and reverse osmosis membrane combine and grinds desulfurization waste liquor
Studying carefully, it is achieved the recycling of elemental sulfur, Ammonium hyposulfite. and ammonium thiocyanate, realize recycling of water resource simultaneously, technique is first
Entering, separation efficiency is high.But owing to film itself is expensive, operating process needs to carry out under certain pressure conditions, and
Film is the most blocked and pollutes, and runs and maintenance cost is high, and the ammonium sulfate in waste water is not effectively addressed in addition.
Summary of the invention
It is an object of the invention to provide the processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid, to carry further
High salt extraction rate and purity salt, optimizing process, reduces cost, it is thus achieved that the ammonium thiocyanate of high-quality and ammonium sulfate product, it is achieved
The full constituent of desulfurization waste liquor utilizes.
For achieving the above object, the technical solution adopted in the present invention is as follows.
The processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid, described method is to adopt for existing coke-stove gas
During removing hydrogen sulfide with ammonia process wet oxidation, produced desulfurization waste liquor is carried out, and concrete grammar step is as follows:
(1) adding activated carbon in ammonia process of desulfurization waste liquid, stirring carries out desolventing technology, filters afterwards, and the desulfurization after being decoloured is given up
Liquid, filtering residue is sent to coal yard coal-blending coking；
(2) desulfurization waste liquor after decolouring is added reactor with sulphuric acid, stir and add oxidant, by evaporation, be dried, obtain
Pretreatment salt-mixture, steam condensate is sent to biochemical workshop section and processes；
(3) pretreatment salt-mixture feeding is once extracted still, and to extracting, still adds liquid SO2, it is stirred simultaneously, it is thus achieved that
Extracting solution and residue；
(4) extracting solution of step (3) is sent into separator, be depressurized to normal pressure, liquid SO through pressure-control valve2Gasification,
To ammonium thiocyanate solid and SO2Gas, it is thus achieved that SO2It is sent to SO after gas is pressurized2Storage tank reuses；
(5) residue of step (3) is delivered to second extraction still, add liquid SO2, extract under certain extraction conditions,
Being stirred simultaneously, extract gained solution and repeat step (4) process, remaining solid residue is ammonium sulfate solids.
The additional technical feature of technique scheme is as follows.
The consumption of described activated carbon is the 1% ~ 5% of desulfurization waste liquor quality, and the condition of described decolouring is bleaching temperature 20 ~ 80
DEG C, bleaching time 0.5 ~ 3h.
The addition of described sulphuric acid is that every cubic metre of desulfurization waste liquor adds 75% ~ 98% sulphuric acid 15 ~ 35 L.
Described oxidant is one or more in air, oxygen and hydrogen peroxide, and the addition of described oxidant is that oxygen divides
Pressure 1.20～2.10 MPa, 30 wt.% H2O2Being 1:10 ~ 1:50 with desulfurization waste liquor volume ratio, the response time is 20 ~ 120 min,
Reaction temperature is 50 ~ 200 DEG C.
During described once extraction, liquid SO2Dosage be that every kilogram of salt-mixture adds 0.60 ~ 1.80 L, institute
State the condition of extraction be Extracting temperature be 10～50 DEG C, extracting pressure is 102～842 kPa, and extraction time is 10～120
min。
During described second extraction, liquid SO2Dosage is that every kilogram of salt-mixture adds 0.18 ~ 0.54 L, described
Extract condition be Extracting temperature be 10～50 DEG C, DEG C, extract pressure be 102～842 kPa, extraction time is 10～120
min。
Implement the processing method of inorganic salt resource in a kind of ammonia process of desulfurization waste liquid of the above-mentioned offer of the present invention, with existing skill
Art is compared, and has the following advantages that and highlights effect.
This method utilizes the desulfurization waste liquor after the decolouring of sulphuric acid, oxidizer treatment, by the Ammonium hyposulfite. in desulfurization waste liquor, sulfur
Compound, elemental sulfur etc. are oxidized to ammonium sulfate, retain ammonium thiocyanate, it is achieved that the full constituent of desulfurization waste liquor inorganic salt utilizes, and improve
Resource utilization, improves economic benefit.
This method utilizes liquid sulfur dioxide to extract after pretreatment the ammonium thiocyanate in salt-mixture, separates ammonium sulfate and sulfur cyanogen
Acid ammonium, it is gas recycling that liquid sulfur dioxide solution pressure rises to atmospheric gasification, simplifies the flow process extracting inorganic salts,
Extraction process is simple, and extraction ratio is high, and process energy consumption is low.
This method utilize liquid sulfur dioxide extract ammonium thiocyanate, isolated ammonium thiocyanate and ammonium sulfate product,
Product purity is high, and quality is good.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of this method.
Specific implementation method
Below the specific implementation method of the present invention is further illustrated.
The processing method of inorganic salt resource, the method in above-mentioned the provided a kind of ammonia process of desulfurization waste liquid of the present invention are provided
Implementation as follows:
A, adding a certain amount of activated carbon carry out desolventing technology in ammonia process of desulfurization waste liquid, its consumption is the 1% of desulfurization waste liquor quality
~ 5%, at bleaching temperature 20 ~ 80 DEG C, bleaching time 0.5 ~ 3 h, carry out desolventing technology under conditions of being kept stirring for, then carry out
Filtering, desulfurization waste liquor after being decoloured, filtering residue is sent to coal yard coal-blending coking.
B, ammonia process of desulfurization waste liquid and 75% ~ 98% sulphuric acid being added reactor, sulphuric acid addition is every cubic metre of desulfurization waste liquor
Adding 75% ~ 98 wt.% sulphuric acid 15 ~ 35 L, and add one or more in air, oxygen, hydrogen peroxide, its addition is oxygen
Dividing potential drop 1.20～2.10 MPa, 30 wt.% H2O2It is 1:10 ~ 1:50 with salt-mixture mass ratio, is 20 ~ 120 in the response time
Min, reaction temperature is reacted under conditions of being 50 ~ 200 DEG C, is stirred simultaneously, incites somebody to action solution evaporation after reacting, is dried,
Salt-mixture after pretreatment, steam condensation is sent to biochemical workshop section and is processed.
C, salt-mixture after pretreatment is sent into and once extracts in still, still adds liquid SO to extracting simultaneously2, liquid SO2Throw
Dosage is that every kilogram of salt-mixture adds 0.60 ~ 1.80 L, is 10～50 DEG C at Extracting temperature, and extracting pressure is 102～842
KPa, extraction time is to extract under conditions of 10～120 min, is stirred simultaneously, once extracted gained solution and
Residue.
D, will once extract gained liquid and be rejected in separator by once extracting still liquid outlet opening, through pressure-control valve
It is depressurized to normal pressure, liquid SO2Gasification, obtains ammonium thiocyanate solid and SO2Gas, obtained SO2Gas is sent to SO2Storage tank weight
Multiple utilization.
E, discharge residue obtained for step C by extracting bottom portion solids exit mouth, deliver to second extraction still, to second extraction
Still adds a certain amount of liquid SO2, liquid SO2Dosage is that every kilogram of salt-mixture adds 0.18 ~ 0.54 L, at Extracting temperature
Being 10～50 DEG C, extracting pressure is 102～842 kPa, and extraction time is to extract under conditions of 10～120 min, extracts
Gained solution repeats the process of step D, residue obtained for ammonium sulfate solids.
Technique scheme is to utilize the ammonium thiocyanate in desulfurization waste liquor to be soluble in liquid sulfur dioxide, and ammonium sulfate is insoluble
In the character of liquid sulfur dioxide, after desulfurization waste liquor is first evaporated with after sulphuric acid, oxidant reaction treatment, is dried to obtain pretreatment
Salt-mixture, reusable liquid sulfur dioxide fully extracts gained salt-mixture, remaining solid i.e. ammonium sulfate, and liquid is close to condition of normal pressure
Under, sulfur dioxide gasifies, recycles, and remaining solid is ammonium thiocyanate.
The detailed description of the invention of the present invention is further illustrated below by specific embodiment.
Embodiment 1
Coking desulfurization waste liquor used by the present embodiment is that coke-oven plant's coke gas uses desulfurization produced by HPF method removing hydrogen sulfide
Waste liquid, takes 500 mL desulfurization waste liquors, and this desulfurization waste liquor is mainly composed of ammonium thiocyanate, Ammonium hyposulfite., suspension sulfur, PDS, dissociates
Ammonia, refers to table 1.
Table 1 desulfurization waste liquor mainly comprises table
| Ammonium hyposulfite. g L<sup>-1</sup> | Ammonium thiocyanate g L<sup>-1</sup> | Suspension sulfur g L<sup>-1</sup> | PDS(ppm) | Free ammonia g L<sup>-1</sup> | pH |
| 90.32 | 140.68 | 0.87 | 49.24 | 5.71 | 8.22 |
The first step, adds 5 g activated carbons in 500 mL ammonia process of desulfurization waste liquids, stirs 3 h under conditions of temperature is 20 DEG C,
Then desulfurization waste liquor after decolouring it is filtrated to get.
Second step, adds reactor by the sulphuric acid of desulfurization waste liquor after above-mentioned decolouring and 7.50 mL98 wt.%, and to reaction
Being filled with air in device, at partial pressure of oxygen 1.20 MPa, temperature reacts 120 min under conditions of being 50 DEG C, simultaneously in course of reaction
It is kept stirring for reaction terminating.To solution evaporation after reacting, be dried, obtain salt-mixture 155.90 g after pretreatment.
3rd step, sends into salt-mixture after above-mentioned pretreatment and once extracts in still, adds 94 mL liquid in extraction still simultaneously
State SO2, it is 10 DEG C in temperature, extracting pressure is to extract 120 min under conditions of 102 kPa, is stirred simultaneously, obtains one
Secondary extraction gained solution and residue.
4th step, will once extract gained liquid and be discharged in separator by once extracting still liquid outlet opening, through pressure
Control valve is depressurized to normal pressure, liquid SO2Gasification, obtains ammonium thiocyanate solid 47.78 g and SO2Gas, obtained SO2Gas
SO it is sent to after pressurized2Storage tank reuses.
5th step, is delivered to second extraction still by residue obtained for step 3 by once extracting the solids exit mouth discharge of bottom portion,
28 mL liquid SO are added in second extraction still2, it is 10 DEG C in temperature, extracting pressure is extraction 120 under conditions of 102 kPa
Min, extracts gained solution and repeats step 4 process, obtain ammonium thiocyanate solid 14.04 g, remaining solid i.e. ammonium sulfate 89.08
g。
Embodiment 2
Coking desulfurization waste liquor used by the present embodiment is that coke-oven plant's coke gas uses desulfurization produced by HPF method removing hydrogen sulfide
Waste liquid, takes 500 mL desulfurization waste liquors, and this desulfurization waste liquor is mainly composed of ammonium thiocyanate, Ammonium hyposulfite., suspension sulfur, PDS, dissociates
Ammonia, refers to table 2.
Table 2 desulfurization waste liquor mainly comprises table
| Ammonium hyposulfite. g L<sup>-1</sup> | Ammonium thiocyanate g L<sup>-1</sup> | Suspension sulfur g L<sup>-1</sup> | PDS(ppm) | Free ammonia g L<sup>-1</sup> | pH |
| 96.72 | 151.80 | 0.88 | 43.66 | 5.58 | 8.12 |
The first step, adds 25 g activated carbons in 500 mL ammonia process of desulfurization waste liquids, stirs under conditions of temperature is 50 DEG C
0.5h, is then filtrated to get desulfurization waste liquor after decolouring.
Second step, adds reactor by desulfurization waste liquor after above-mentioned decolouring and 12.50 mL75 wt.% sulphuric acid, and adds 30
wt.% H2O250 mL, react 20 min under conditions of temperature is 200 DEG C, are kept stirring for reaction in course of reaction simultaneously
Terminate.Solution evaporation after reaction, it is dried, obtains salt-mixture 167.16 g after pretreatment.
3rd step, sends into salt-mixture after above-mentioned pretreatment and once extracts in still, adds 200 mL in extraction still simultaneously
Liquid SO2, it is 50 DEG C in temperature, extracting pressure is to extract 10 min under conditions of 842 kPa, is stirred simultaneously, obtains one
Secondary extraction gained solution and residue.
4th step, will once extract gained liquid and be discharged in separator by once extracting still liquid outlet opening, through pressure
Control valve is depressurized to normal pressure, liquid SO2Gasification, obtains ammonium thiocyanate solid 55.22 g and SO2Gas, obtained SO2Gas
SO it is sent to after pressurized2Storage tank reuses.
5th step, is delivered to second extraction still by residue obtained for step 3 by once extracting the solids exit mouth discharge of bottom portion,
60 mL liquid SO are added in second extraction still2, it is 50 DEG C in temperature, extracting pressure is extraction 10 under conditions of 842 kPa
Min, extracts gained solution and repeats step 4 process, obtain ammonium thiocyanate solid 18.41 g, remaining solid i.e. ammonium sulfate 93.53
g。
Embodiment 3
Coking desulfurization waste liquor used by the present embodiment is that coke-oven plant's coke gas uses desulfurization produced by HPF method removing hydrogen sulfide
Waste liquid, takes 500 mL desulfurization waste liquors, and this desulfurization waste liquor is mainly composed of ammonium thiocyanate, Ammonium hyposulfite., suspension sulfur, PDS, dissociates
Ammonia, refers to table 3.
Table 3 desulfurization waste liquor mainly comprises table
| Ammonium hyposulfite. g L<sup>-1</sup> | Ammonium thiocyanate g L<sup>-1</sup> | Suspension sulfur g L<sup>-1</sup> | PDS(ppm) | Free ammonia g L<sup>-1</sup> | pH |
| 58.72 | 164.68 | 0.69 | 40.65 | 5.03 | 8.16 |
The first step, adds 15 g activated carbons in 500 mL ammonia process of desulfurization waste liquids, stirs 1.5 under conditions of temperature is 80 DEG C
H, is then filtrated to get desulfurization waste liquor after decolouring.
Second step, adds reactor by desulfurization waste liquor after above-mentioned decolouring and 10 mL98 wt.% sulphuric acid, and in reactor
Being filled with oxygen, at partial pressure of oxygen 2.10 MPa, temperature reacts 60 min under conditions of being 130 DEG C, keeps in course of reaction simultaneously
Stirring terminates to reaction.To solution evaporation after reacting, be dried, obtain salt-mixture 139.71 g after pretreatment.
3rd step, sends into salt-mixture after above-mentioned pretreatment and once extracts in still, adds 252 mL in extraction still simultaneously
Liquid SO2, it is 30 DEG C in temperature, extracting pressure is to extract 60 min under conditions of 458 kPa, is stirred simultaneously, obtains one
Secondary extraction gained solution and residue.
4th step, will once extract gained liquid and be discharged in separator by once extracting still liquid outlet opening, through pressure
Control valve is depressurized to normal pressure, liquid SO2Gasification, obtains ammonium thiocyanate solid 64.55 g and SO2Gas, obtained SO2Gas
SO it is sent to after pressurized2Storage tank reuses.
5th step, is delivered to second extraction still by residue obtained for step 3 by once extracting the solids exit mouth discharge of bottom portion,
75 mL liquid SO are added in second extraction still2, it is 30 DEG C in temperature, extracting pressure is extraction 60 under conditions of 458 kPa
Min, extracts gained solution and repeats step 4 process, obtain ammonium thiocyanate solid 16.14 g, remaining solid i.e. ammonium sulfate 59.02
g。
Claims (6)
1. a processing method for inorganic salt resource in ammonia process of desulfurization waste liquid, described method is to use for existing coke-stove gas
During ammonia process wet oxidation removing hydrogen sulfide, produced desulfurization waste liquor is carried out, and concrete grammar step is as follows:
(1) adding activated carbon in ammonia process of desulfurization waste liquid, stirring carries out desolventing technology, filters afterwards, and the desulfurization after being decoloured is given up
Liquid, filtering residue is sent to coal yard coal-blending coking；
(2) desulfurization waste liquor after decolouring is added reactor with sulphuric acid, stir and add oxidant, by evaporation, be dried, obtain
Pretreatment salt-mixture, steam condensate is sent to biochemical workshop section and processes；
(3) pretreatment salt-mixture feeding is once extracted still, and to extracting, still adds liquid SO2, it is stirred simultaneously, it is thus achieved that
Extracting solution and residue；
(4) extracting solution of step (3) is sent into separator, be depressurized to normal pressure, liquid SO through pressure-control valve2Gasification, obtains
Ammonium thiocyanate solid and SO2Gas, it is thus achieved that SO2It is sent to SO after gas is pressurized2Storage tank reuses；
(5) residue of step (3) is delivered to second extraction still, add liquid SO2, extract under certain extraction conditions, with
Time be stirred, extract gained solution repeat step (4) process, remaining solid residue is ammonium sulfate solids.
2. the method for claim 1, the consumption of described activated carbon is the 1% ~ 5% of desulfurization waste liquor quality, described decolouring
Condition is bleaching temperature 20 ~ 80 DEG C, bleaching time 0.5 ~ 3h.
3. the method for claim 1, the addition of described sulphuric acid is that every cubic metre of desulfurization waste liquor adds 75% ~ 98% sulphuric acid
15~35 L。
4. the method for claim 1, described oxidant is one or more in air, oxygen and hydrogen peroxide, described
The addition of oxidant is partial pressure of oxygen 1.20～2.10 MPa, 30 wt.% H2O2It is 1:10 ~ 1:50 with desulfurization waste liquor volume ratio,
Response time is 20 ~ 120 min, and reaction temperature is 50 ~ 200 DEG C.
5. the method for claim 1, during described once extraction, liquid SO2Dosage be every kilogram of salt-mixture
Add 0.60 ~ 1.80 L, the condition of described extraction be Extracting temperature be 10～50 DEG C, extract pressure be 102～842 kPa, carry
The time of taking is 10～120 min.
6. the method for claim 1, during described second extraction, liquid SO2Dosage be every kilogram of salt-mixture
Add 0.18 ~ 0.54 L, the condition of described extraction be Extracting temperature be 10～50 DEG C, extract pressure be 102～842 kPa, carry
The time of taking is 10～120 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108439430A (en) * | 2018-05-10 | 2018-08-24 | 扬州康龙环保工程有限公司 | The method that ammonium thiocyanate and ammonium sulfate are extracted in oven gas ammonia process of desulfurization waste liquid |
| CN108516566A (en) * | 2018-04-26 | 2018-09-11 | 太原理工大学 | The method for preparing cuprous sulfocyanide using ammonia process coking desulfurization waste liquor |
| CN117049754A (en) * | 2023-10-12 | 2023-11-14 | 中南大学 | Recycling treatment method of desulfurization waste liquid and preparation of sulfur and sodium sulfite |
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| JPS4986268A (en) * | 1972-12-22 | 1974-08-19 | ||
| CN103011201A (en) * | 2012-12-28 | 2013-04-03 | 安徽工业大学 | Method for extracting ammonium thiocyanate from ammonia-process desulfurization waste liquid by oxidation process |
| CN105036438A (en) * | 2015-07-14 | 2015-11-11 | 太原理工大学 | Harmless treatment method for sodium alkali desulfurization waste solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4986268A (en) * | 1972-12-22 | 1974-08-19 | ||
| CN103011201A (en) * | 2012-12-28 | 2013-04-03 | 安徽工业大学 | Method for extracting ammonium thiocyanate from ammonia-process desulfurization waste liquid by oxidation process |
| CN105036438A (en) * | 2015-07-14 | 2015-11-11 | 太原理工大学 | Harmless treatment method for sodium alkali desulfurization waste solution |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516566A (en) * | 2018-04-26 | 2018-09-11 | 太原理工大学 | The method for preparing cuprous sulfocyanide using ammonia process coking desulfurization waste liquor |
| CN108439430A (en) * | 2018-05-10 | 2018-08-24 | 扬州康龙环保工程有限公司 | The method that ammonium thiocyanate and ammonium sulfate are extracted in oven gas ammonia process of desulfurization waste liquid |
| CN108439430B (en) * | 2018-05-10 | 2020-08-25 | 扬州康龙环保工程有限公司 | Method for extracting ammonium thiocyanate and ammonium sulfate from coke oven gas ammonia-process desulfurization waste liquid |
| CN117049754A (en) * | 2023-10-12 | 2023-11-14 | 中南大学 | Recycling treatment method of desulfurization waste liquid and preparation of sulfur and sodium sulfite |
| CN117049754B (en) * | 2023-10-12 | 2024-02-23 | 中南大学 | Recycling treatment method of desulfurization waste liquid and preparation of sulfur and sodium sulfite |
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