CN112340911A - Method for recycling desulfurization waste liquid - Google Patents
Method for recycling desulfurization waste liquid Download PDFInfo
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- CN112340911A CN112340911A CN202011046050.5A CN202011046050A CN112340911A CN 112340911 A CN112340911 A CN 112340911A CN 202011046050 A CN202011046050 A CN 202011046050A CN 112340911 A CN112340911 A CN 112340911A
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- 239000007788 liquid Substances 0.000 title claims abstract description 174
- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 62
- 230000023556 desulfurization Effects 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 23
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 11
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 9
- 150000003839 salts Chemical group 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000004042 decolorization Methods 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 235000017550 sodium carbonate Nutrition 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 11
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for recycling desulfurization waste liquid, belongs to the field of wastewater treatment, and can solve the problems that two kinds of desulfurization waste liquid cannot be simultaneously recycled and evolved, and the recycled matter is low in purity and difficult to directly utilize in the prior art. The method for recycling the desulfurization waste liquid at least comprises the steps of adding sodium carbonate into the ammonium salt desulfurization waste liquid, mixing with the sodium salt desulfurization waste liquid, then carrying out conversion, and recycling the generated carbon dioxide and ammonia gas in the process. The method is used for recycling the ammonium salt and sodium salt desulfurization waste liquid with high quality.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for recycling desulfurization waste liquid.
Background
In the industrial production process such as coking, the treatment step of desulfurization is difficult to avoid, and the treatment of the desulfurization waste liquid after desulfurization becomes a problem to be solved urgently.
The desulfurization waste liquid mainly comprises ammonium salt desulfurization waste liquid and sodium salt desulfurization waste liquid, and the two desulfurization waste liquids contain a large amount of thiocyanate, thiosulfate, sulfate and other toxic and harmful substances. If the desulfurization waste liquid is not treated and directly discharged, the problem of environmental pollution can be caused; at the same time, recoverable compounds in the desulfurization waste stream are wasted.
In view of the above, researchers have developed various desulfurization waste liquid treatment technologies to recover sulfur-containing substances such as sulfate and thiocyanate. The existing desulfurization waste liquid treatment technology mainly aims at single ammonium salt or sodium salt desulfurization waste liquid, and the adopted treatment mode is generally a gradient crystallization salt extraction method or a solvent extraction method, but substances extracted by the method have low purity and are difficult to directly use, and the latter treatment mode has high treatment cost and great danger. With the development of industry, the same production line can simultaneously produce ammonium salt desulfurization waste liquid and sodium salt desulfurization waste liquid, and the current treatment technology aiming at single desulfurization waste water cannot meet the actual industrial requirement.
In view of the above, there is a need to improve the defects that the two desulfurization waste liquids cannot be recovered and evolved at the same time and the recovered product has low purity and is difficult to be directly used in the prior art, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for recycling ammonium salt and sodium salt desulfurization waste liquid with high quality.
The technical scheme for realizing the purpose of the invention is as follows:
a method for recycling desulfurization waste liquid at least comprises the following steps:
adding sodium carbonate into the ammonium salt desulfurization waste liquid, mixing with the sodium salt desulfurization waste liquid, and then carrying out conversion, wherein the reaction temperature of the conversion is 60-70 ℃, and the generated carbon dioxide and ammonia gas are recovered in the process.
As a further improvement of the present invention,
and the carbon dioxide and ammonia gas generated in the conversion process are washed and absorbed by water and then are utilized.
Further comprising the steps of:
filtering after the conversion is finished to obtain insoluble waste residues and primary clear liquid;
adjusting the pH value of the primary clear liquid to be acidic, and then carrying out an oxidation reaction to obtain an oxidation liquid, wherein the reaction temperature of the oxidation reaction is 90-100 ℃;
filtering the oxidation solution to obtain elemental sulfur and secondary clear liquid;
adding fluosilicic acid into the secondary clear liquid for reaction, and filtering to obtain sodium fluosilicate and a tertiary clear liquid;
adjusting the pH value of the third clear liquid to be alkaline, and then filtering to obtain waste salt residues and fourth clear liquid;
adding barium hydroxide into the fourth clear liquid for reaction, and then filtering to obtain solid barium sulfate and the fifth clear liquid;
and concentrating and crystallizing the fifth clear liquid, and dehydrating to obtain sodium thiocyanate.
Adjusting the pH of the primary clear liquid to be acidic, specifically:
and adding sulfuric acid into the primary clear liquid, adjusting the pH value of the primary clear liquid to 2-3, and keeping the pH value until the oxidation reaction is finished.
Adjusting the pH of the third clear liquid to be alkaline, specifically:
and adding sodium hydroxide into the third clear liquid, and adjusting the pH value to 9-11.
And (3) adjusting the pH value of the third clear liquid to be alkaline, reducing the temperature to 80-90 ℃, and then filtering.
And adding activated carbon into the four times of clear liquid for decoloring, and filtering the activated carbon after the reaction is finished.
And concentrating the five times of clear liquid to a concentration of 700-800 g/L.
And crystallizing the five times of clear liquid after the concentration treatment, and simultaneously cooling the clear liquid.
And keeping the temperature of the five times of clear liquid at 50-60 ℃ in the temperature reduction treatment process.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for recycling the desulfurization waste liquid, provided by the invention, after a series of simpler processes are carried out, the ammonium salt and the sodium salt in the desulfurization waste liquid can be simultaneously recycled, and sodium thiocyanate, sodium sulfate and recyclable ammonia gas with high purity and high added value are obtained; in addition, elemental sulfur can be recovered in the treatment process, and substances such as sodium fluosilicate and the like are prepared by using a small amount of residual sodium sulfate in the waste liquid, so that the utilization rate of inorganic salts in the desulfurization waste liquid and the environmental-friendly purification rate are improved; moreover, the treatment process is relatively simple, the cost is relatively low, the waste is changed into valuable, the economic benefit is relatively high, the treatment mode is economic and effective, a feasible method is provided for the combined treatment of ammonium salt and sodium salt in the desulfurization waste liquid and the efficient resource utilization of the ammonium salt and the sodium salt, and the industrial popularization is facilitated.
Drawings
FIG. 1 is a process flow diagram of the method for recovering and reusing a desulfurization waste liquid according to the present invention.
Detailed Description
The present invention is described in detail with reference to the embodiments shown in the drawings, but it should be understood that these embodiments are not intended to limit the present invention, and those skilled in the art should understand that functional, methodological, or structural equivalents or substitutions made by these embodiments are within the scope of the present invention.
Referring to fig. 1, fig. 1 is a process flow diagram of the method for recycling desulfurized waste liquid according to the present invention, including the steps of:
s1, adding sodium carbonate into the ammonium salt desulfurization waste liquid, mixing with the sodium salt desulfurization waste liquid, and then converting at the temperature of 60-70 ℃, wherein the generated carbon dioxide and ammonia gas are recovered in the process;
within the conversion temperature range of 60-70 ℃, the reaction speed is correspondingly improved along with the improvement of the reaction temperature, and the conversion rate is also slightly improved; in addition, within the temperature range, the heating temperature can be just kept by utilizing the industrial waste heat, so that the effective utilization of the industrial waste heat is realized, and the energy is saved.
Because a large amount of ammonium ions and Ca exist in the ammonium salt desulfurization waste liquid2+、S2-、S2O3 2-、SO4 2-The resource recovery of the ammonium salt is too saturated, the profit is low, and the ammonium salt and the sodium salt desulfurization waste liquid need different treatment processes for treatment, so the method selects to convert the ammonium salt into the sodium salt, and particularly converts the ammonium salt into the sodium salt by adjusting the pH to be alkaline (wherein, the pH can be adjusted by alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like). Meanwhile, a small amount of impurity ions such as calcium ions exist in the waste liquid, the calcium ions in the waste liquid can be well removed by using carbonate, and in order to avoid introducing other ions, sodium carbonate is selected, and the price of the sodium carbonate is relatively low, so that the pH value can be adjusted and the impurity ions such as the calcium ions in the waste liquid can be removed by selecting the sodium carbonate. In addition, sodium carbonate is added into the ammonium salt desulfurization waste liquid firstly, so that the sodium carbonate can be converted into sodium salt in one step, and the sodium salt can be treated in the subsequent treatment steps, so that the treatment difficulty is simplified. The carbon dioxide and ammonia gas generated by the reaction can be utilized after being washed and absorbed, so that the economic value is increased. Since both carbon dioxide and ammonia are soluble in water, it is preferred that the solution is also subjected to a heat treatment during this process to take advantage of the recovery of carbon dioxide and ammonia.
The reaction equation occurring in this step is as follows:
(NH4)2S+Na2CO3→(NH4)2CO3+Na2S；
(NH4)2S2O3+Na2CO3→(NH4)2CO3+Na2S2O3；
CaSO4+Na2CO3→CaCO3↓+(NH4)2SO4；
(NH4)2CO3→2NH3↑+CO2↑+H2O。
s2, filtering after the conversion is finished to obtain insoluble waste residues and primary clear liquid;
the step is mainly used for filtering insoluble substances such as waste residues in the desulfurization waste liquid, such as materials, dust and the like mixed in the desulfurization waste liquid, and calcium carbonate precipitate obtained by reaction. Preferably, in order to improve the filtering effect, the invention can select a suction filtration mode for filtering.
S3, adjusting the pH value of the primary clear liquid to be acidic, and then carrying out oxidation reaction to obtain oxidation liquid, wherein the reaction temperature of the oxidation reaction is 90-100 ℃;
compared with a higher reaction temperature, the reaction temperature of 90-100 ℃ can achieve a better oxidation reaction effect, and the reaction temperature is easy to realize and can save energy.
Preferably, sulfuric acid (preferably dilute sulfuric acid) can be added into the primary clear liquid, the pH value of the primary clear liquid is adjusted to be 2-3, and the primary clear liquid is kept until the whole oxidation reaction is finished. Because the desulfurization waste liquid contains sulfate ions, the pH of the primary clear liquid is adjusted by adding sulfuric acid in order to avoid introducing new elements.
The chemical reaction equation that occurs for this step is as follows:
2Na2S+O2+H2O→4NaOH+S↓；
2NaOH+H2SO4→Na2SO4+2H2O；
2Na2S2O3+O2→2Na2SO4+S↓。
s4, filtering the oxidation liquid to obtain elemental sulfur and secondary clear liquid;
and (3) filtering residues after the oxidation reaction, namely the elemental sulfur and a large amount of solid sodium sulfate which reaches the dissolution limit and cannot be dissolved, recycling, wherein secondary clear liquid comprises saturated solution of sodium sulfate. The recovered elemental sulfur and the solid sodium sulfate have high purity, and can be directly used after separation, thereby improving the enterprise profit and realizing the reasonable recovery and utilization of resources.
S5, adding fluosilicic acid into the secondary clear liquid for reaction, and filtering to obtain sodium fluosilicate and a tertiary clear liquid;
reacting fluosilicic acid with sodium ions in the secondary clear liquid to generate solid sodium fluosilicate, and drying to obtain the final product, wherein the tertiary clear liquid is acidic.
S6, adjusting the pH value of the tertiary clear liquid to be alkaline, and then filtering to obtain waste salt residues and a quaternary clear liquid;
preferably, the third clear solution may be subjected to a concentration treatment before the pH is adjusted.
And preferably, adding sodium hydroxide into the third clear liquid, and adjusting the pH value to 9-11. Since the desulfurization waste liquid of the present invention is currently a sodium salt desulfurization waste liquid, sodium hydroxide is selected in order to avoid introducing new elements when the pH thereof is adjusted to be alkaline.
Furthermore, because the pH adjustment process is an exothermic reaction, the temperature is preferably reduced to 80-90 ℃, and then the filtration treatment is carried out. The temperature reduction may be performed by heat exchange such as water cooling, which is not limited in the present invention.
S7, adding barium hydroxide into the fourth clear liquid for reaction, and then filtering to obtain solid barium sulfate and the fifth clear liquid;
because the barium sulfate is a water-insoluble substance, barium hydroxide is selectively added, and the introduced barium ions can be removed by filtration after reaction.
The chemical reaction equation that occurs for this step is as follows:
Na2SO4+Ba(OH)2→BaSO4↓+2NaOH。
further, the invention adds barium hydroxide and active carbon into the four times of clear liquid for decolorization at the same time, and then filters the active carbon after the reaction is finished.
And S8, concentrating and crystallizing the fifth clear liquid, and dehydrating to obtain sodium thiocyanate.
Further, the five times of clear liquid is concentrated to the concentration of 700 g/L-800 g/L, and the concentration is improved, so that the subsequent treatment is facilitated.
Furthermore, the five times of clear liquid after the concentration treatment is crystallized and is cooled at the same time. Specifically, the temperature of the clear liquid is kept at 50-60 ℃ for five times in the temperature reduction process.
It will be understood by those skilled in the art that the amount of the reactant materials added in the present invention depends on the ion content of the solution to be reacted therewith, and the amount of the reactant materials added can be determined according to the ion concentration of the solution, and the present invention is not limited to specific amount of the reactant materials.
As can be seen from the above description of the solution of the present invention, compared with the prior art, the present invention has at least the following advantages:
firstly, the merging treatment of ammonium salt and sodium salt in the desulfurization waste liquid is realized, so that two sets of treatment processes can be merged into one set of treatment process for treatment, and sodium thiocyanate and sodium sulfate products with high added values are recycled;
secondly, the resource utilization rate of other inorganic salts in the desulfurization waste liquid is improved, elemental sulfur and sodium fluosilicate can be sold in the resource process, and ammonia can be recycled, so that the enterprise income is increased, and the desulfurization cost is reduced;
thirdly, the method has the advantages of simple process, relatively low cost and relatively high economic benefit, and provides meaningful reference for the combined treatment of ammonium salt and sodium salt in the desulfurization waste liquid and the development of the high-efficiency resource utilization technology thereof.
The present invention will be described in detail with reference to examples.
Example 1:
the method for recycling the desulfurization waste liquid provided by the embodiment comprises the following steps:
s1, adding soda ash into the ammonium salt solution, mixing with the sodium salt solution, placing the mixture into a conversion kettle for conversion at the conversion temperature of 60 ℃, recovering generated carbon dioxide and ammonia gas in the conversion process, and recycling after washing and absorbing;
s2, after the conversion is finished, placing the mixture in a suction filtration tank to obtain insoluble waste residues and primary clear liquid;
s3, adjusting the pH of the primary clear liquid to 2 by using dilute sulfuric acid, and placing the primary clear liquid in an oxidation kettle for oxidation reaction to obtain oxidation liquid, wherein the reaction temperature of the oxidation reaction is 90 ℃;
s4, placing the oxidized liquid obtained in the step S3 in a filter tank, and filtering to obtain elemental sulfur, solid sodium sulfate and secondary clear liquid;
s5, placing the secondary clear liquid obtained in the step S4 in a reaction kettle, adding fluosilicic acid for reaction, placing the solution in a filter tank after the reaction is finished, and obtaining filter residue (sodium fluosilicate) and tertiary clear liquid; drying sodium fluosilicate in an oven to obtain a sodium fluosilicate product;
s6, placing the tertiary clear liquid processed by the S5 into a concentration kettle for concentration, adjusting the pH to 9 by using sodium hydroxide, and placing the tertiary clear liquid into a cooling tank to be cooled to 80 ℃ in the process of adjusting the pH or after adjusting the pH; finally, placing the cooled solution in a filter tank to obtain waste salt residues and a fourth clear liquid;
s7, adding activated carbon and barium hydroxide into the fourth clear liquid obtained in the step S6, and reacting for a period of time; then placing the solution in a filter tank to obtain filter residue barium sulfate and five times of clear liquid;
s8, placing the five times of clear liquid obtained in the S7 in a concentration kettle, concentrating to 700g/L, and cooling to 60 ℃; finally, carrying out suction filtration and dehydration treatment to obtain a solid product sodium thiocyanate.
The purity of the product sodium thiocyanate obtained in the step of S8 was checked to be 94%.
Example 2:
the method for recycling the desulfurization waste liquid provided by the embodiment comprises the following steps:
s1, adding soda ash into the ammonium salt solution, mixing with the sodium salt solution, placing the mixture into a conversion kettle for conversion at the conversion temperature of 65 ℃, recovering generated carbon dioxide and ammonia gas in the conversion process, and recycling after washing and absorbing;
s2, after the conversion is finished, placing the mixture in a suction filtration tank to obtain insoluble waste residues and primary clear liquid;
s3, adjusting the pH of the primary clear liquid to 2.5 by using dilute sulfuric acid, and placing the primary clear liquid in an oxidation kettle for oxidation reaction to obtain an oxidation liquid, wherein the reaction temperature of the oxidation reaction is 95 ℃;
s4, placing the oxidized liquid obtained in the step S3 in a filter tank, and filtering to obtain elemental sulfur, solid sodium sulfate and secondary clear liquid;
s5, placing the secondary clear liquid obtained in the step S4 in a reaction kettle, adding fluosilicic acid for reaction, placing the solution in a filter tank after the reaction is finished, and obtaining filter residue (sodium fluosilicate) and tertiary clear liquid; drying sodium fluosilicate in an oven to obtain a sodium fluosilicate product;
s6, placing the tertiary clear liquid processed by the S5 into a concentration kettle for concentration, adjusting the pH to 10 by using sodium hydroxide, and placing the tertiary clear liquid into a cooling tank to be cooled to 90 ℃ in the process of adjusting the pH or after adjusting the pH; finally, placing the cooled solution in a filter tank to obtain waste salt residues and a fourth clear liquid;
s7, adding activated carbon and barium hydroxide into the fourth clear liquid obtained in the step S6, and reacting for a period of time; then placing the solution in a filter tank to obtain filter residue barium sulfate and five times of clear liquid;
s8, placing the five times of clear liquid obtained in the S7 in a concentration kettle, concentrating to 750g/L, and cooling to 50 ℃; and finally, carrying out filter pressing dehydration treatment to obtain a solid product sodium thiocyanate.
The purity of the product sodium thiocyanate obtained in the step of S8 was checked to be 96%.
Example 3:
the method for recycling the desulfurization waste liquid provided by the embodiment comprises the following steps:
s1, adding soda ash into the ammonium salt solution, mixing with the sodium salt solution, placing the mixture into a conversion kettle for conversion at the conversion temperature of 70 ℃, recovering generated carbon dioxide and ammonia gas in the conversion process, and recycling after washing and absorbing;
s2, after the conversion is finished, placing the mixture in a suction filtration tank to obtain insoluble waste residues and primary clear liquid;
s3, adjusting the pH of the primary clear liquid to 3 by using dilute sulfuric acid, and placing the primary clear liquid in an oxidation kettle for oxidation reaction to obtain an oxidation liquid, wherein the reaction temperature of the oxidation reaction is 100 ℃;
s4, placing the oxidized liquid obtained in the step S3 in a filter tank, and filtering to obtain elemental sulfur, solid sodium sulfate and secondary clear liquid;
s5, placing the secondary clear liquid obtained in the step S4 in a reaction kettle, adding fluosilicic acid for reaction, placing the solution in a filter tank after the reaction is finished, and obtaining filter residue (sodium fluosilicate) and tertiary clear liquid; drying sodium fluosilicate in an oven to obtain a sodium fluosilicate product;
s6, placing the tertiary clear liquid processed by the S5 into a concentration kettle for concentration, adjusting the pH to 11 by using sodium hydroxide, and placing the tertiary clear liquid into a cooling tank to be cooled to 85 ℃ in the process of adjusting the pH or after adjusting the pH; finally, placing the cooled solution in a filter tank to obtain waste salt residues and a fourth clear liquid;
s7, adding activated carbon and barium hydroxide into the fourth clear liquid obtained in the step S6, and reacting for a period of time; then placing the solution in a filter tank to obtain filter residue barium sulfate and five times of clear liquid;
s8, placing the five times of clear liquid obtained in the S7 in a concentration kettle, concentrating to 800g/L, and cooling to 55 ℃; finally, carrying out suction filtration and dehydration treatment to obtain a solid product sodium thiocyanate.
The purity of the product sodium thiocyanate obtained in the step of S8 was checked to be 97%.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A method for recycling desulfurization waste liquid is characterized by at least comprising the following steps:
adding sodium carbonate into the ammonium salt desulfurization waste liquid, mixing with the sodium salt desulfurization waste liquid, and then carrying out conversion, wherein the reaction temperature of the conversion is 60-70 ℃, and the generated carbon dioxide and ammonia gas are recovered in the process.
2. The method for recycling desulfurization waste liquid according to claim 1, wherein carbon dioxide and ammonia gas generated in the conversion process are absorbed by water washing and then utilized.
3. The method for recycling desulfurization waste liquid according to claim 1, further comprising the steps of:
filtering after the conversion is finished to obtain insoluble waste residues and primary clear liquid;
adjusting the pH value of the primary clear liquid to be acidic, and then carrying out an oxidation reaction to obtain an oxidation liquid, wherein the reaction temperature of the oxidation reaction is 90-100 ℃;
filtering the oxidation solution to obtain elemental sulfur and secondary clear liquid;
adding fluosilicic acid into the secondary clear liquid for reaction, and filtering to obtain sodium fluosilicate and a tertiary clear liquid;
adjusting the pH value of the third clear liquid to be alkaline, and then filtering to obtain waste salt residues and fourth clear liquid;
adding barium hydroxide into the fourth clear liquid for reaction, and then filtering to obtain solid barium sulfate and the fifth clear liquid;
and concentrating and crystallizing the fifth clear liquid, and dehydrating to obtain sodium thiocyanate.
4. The method for recycling desulfurization waste liquid according to claim 3, wherein the pH of the primary clear liquid is adjusted to be acidic, specifically:
and adding sulfuric acid into the primary clear liquid, adjusting the pH value of the primary clear liquid to 2-3, and keeping the pH value until the oxidation reaction is finished.
5. The method for recycling desulfurization waste liquid according to claim 3, wherein the pH of the tertiary clear liquid is adjusted to be alkaline, specifically:
and adding sodium hydroxide into the third clear liquid, and adjusting the pH value to 9-11.
6. The method for recycling desulfurization waste liquid according to claim 3 or 5, wherein the temperature of the third clear liquid is lowered to 80 ℃ to 90 ℃ after the pH of the third clear liquid is adjusted to be alkaline, and then the third clear liquid is filtered.
7. The method for recycling desulfurization waste liquid according to claim 3, wherein activated carbon is further added to the fourth-time clear liquid to perform decolorization treatment, and the activated carbon is filtered after the reaction is completed.
8. The method for recycling desulfurization waste liquid according to claim 3, wherein the fifth time clear liquid is concentrated to a concentration of 700g/L to 800 g/L.
9. The method for recovering and reusing a desulfurized waste liquid according to claim 3, wherein said five times of clear liquid after concentration treatment is subjected to temperature reduction treatment simultaneously with crystallization treatment.
10. The method for recycling desulfurization waste liquid according to claim 9, wherein the temperature of the five times of clear liquid is maintained to be 50 ℃ to 60 ℃ in the temperature reduction treatment process.
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