CN114212930B - Method for improving purity of wet desulfurization waste water byproducts - Google Patents
Method for improving purity of wet desulfurization waste water byproducts Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/02—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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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/66—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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 invention discloses a method for controlling the purity of wet desulphurization waste water byproducts, which comprises the steps of adjusting the pH value of wet desulphurization waste water to 6-9, and then mixing the wet desulphurization waste water with ferrous salt for reaction to obtain mixed solution; the mixed solution is concentrated and subjected to solid-liquid separation, the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite products, and the liquid is high-chlorine strong brine. The method can effectively improve the quality of gypsum as a byproduct of wet desulfurization wastewater, replaces the traditional filtering method of the disc vacuum filter, greatly simplifies the operation, and reduces the energy consumption and water consumption; but also can rapidly reduce the ammonia nitrogen concentration in the wet desulfurization wastewater, and avoid the problems of high technical energy consumption, high operation cost and the like of ammonia nitrogen removal by a gaseous membrane method, ammonia nitrogen removal by steam stripping and the like.
Description
Technical Field
The invention relates to a method for improving the purity of wet desulfurization waste water byproducts, in particular to a method for improving the purity of wet desulfurization waste water byproducts by using an ammonium ferrous sulfite method, and belongs to the technical field of wet desulfurization waste water treatment.
Background
The water quality components of the desulfurization wastewater contain various pollutants such as suspended matters, supersaturated sulfite, ammonia nitrogen, heavy metals and the like, wherein the concentration content of the suspended matters is high, the suspended matters and solid wastes such as the heavy metals and the like form harmful sludge, and the harmful sludge is required to be intensively treated by solid waste treatment factories, so that the treatment cost is high. The insoluble suspended matter is gypsum as main component and may be recovered for use in preparing green building material product, such as mortar, etc.
However, the recycled gypsum has higher chloride ion content and very strong coordination capability, and when the concentration of the recycled gypsum is higher, the recycled gypsum can chemically react with magnesium ions and ammonium ions in wastewater to generate water-soluble chloride salt, and the chloride salt is wrapped in the gypsum, so that the quality of the gypsum can be reduced, and the performance and quality of the gypsum and products thereof can be greatly limited, for example, the phenomena of moisture regain and yellowing of the gypsum mortar in the use process can be caused when the gypsum mortar is prepared from the high-chlorine desulfurization gypsum. And can also react with steel bars and the like electrochemically, so that the steel bars are corroded, and serious safety problems are caused. Therefore, the method reduces the content of chloride in the gypsum, improves the quality of the chlorine-containing gypsum, and is important for gypsum treatment and resource utilization.
Under the current technical conditions, an effective method for reducing the chloride salt content in the desulfurized gypsum is to wash and filter the gypsum filter cake with a large amount of flushing water. The gypsum is washed by a large amount of washing water, and the content of chloride ions can be effectively reduced, but the quality of the gypsum is affected, and the problems of high energy consumption, high washing water consumption, complex operation, high cost and the like exist. Therefore, the research of a method for controlling the purity of byproducts in wet desulfurization wastewater has important practical significance.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a method for improving the purity of wet desulfurization waste water byproducts, which can not only effectively improve the quality of wet desulfurization waste water byproduct gypsum, but also replace the traditional filtering method of a disc vacuum filter, thereby greatly simplifying the operation and reducing the energy consumption and water consumption; but also can rapidly reduce the ammonia nitrogen concentration in the wet desulfurization wastewater, and avoid the problems of high technical energy consumption, high operation cost and the like of ammonia nitrogen removal by a gaseous membrane method, ammonia nitrogen removal by steam stripping and the like.
In order to achieve the technical aim, the invention provides a method for improving the purity of wet desulphurization waste water byproducts, which comprises the steps of adjusting the pH value of wet desulphurization waste water to 6-9, and then mixing with ferrous salt for reaction to obtain mixed solution; the mixed solution is concentrated and subjected to solid-liquid separation, the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite products, and the liquid is high-chlorine strong brine.
The wet desulfurization waste water mainly contains sulfate radical, sulfite radical, calcium ion, ammonium ion, chloride ion and the like, and the prior art mainly obtains gypsum products by concentrating the wet desulfurization waste water, but the concentration of ammonia nitrogen is increased to 10-20 g/L in the concentrating process of the wet desulfurization waste water, the high-concentration ammonia nitrogen can be combined with the chloride ion and a small amount of impurity magnesium ion in the waste water to form magnesium ammonium chloride crystal salt, and the magnesium ammonium chloride crystal salt is doped in the calcium sulfate products in a coprecipitation mode, so that the content of the chloride ion in the gypsum products can be increased, and the quality of gypsum is affected. The key of the technical scheme of the invention is that by strictly controlling the pH condition of the wet desulfurization wastewater and matching with ferrous salt, ammonia nitrogen in the wet desulfurization wastewater is preferably converted with sulfite radical and ferrous ion into a relatively stable ferrous ammonium sulfite product under proper conditions, thereby effectively inhibiting the formation of magnesium ammonium chloride, leading chloride ion to be still enriched in water solution as soluble salt and greatly reducing the chlorine content of gypsum product.
As a preferable scheme, the wet desulfurization wastewater contains 2100-3200 mg/L sulfate, 800-2000 mg/L sulfite, 2000-3100 mg/L calcium ion, 1000-2500 mg/L ammonium ion and 15000-20000 mg/L chloride ion. According to the technical scheme, the characteristic that the wet desulfurization wastewater is rich in sulfite radical and ammonium ion is utilized, and ammonia nitrogen can be converted into stable ferrous ammonium sulfite only by introducing a proper amount of ferrous ion, so that the ammonia nitrogen can be effectively prevented from being separated out in the form of magnesium ammonium chloride.
As a preferable scheme, the ferrous salt is at least one of ferrous sulfate heptahydrate, ferrous chloride tetrahydrate and ferrous nitrate. The technical scheme of the invention mainly utilizes ferrous ions to convert ammonia nitrogen and sulfite ions, and theoretically common water-soluble ferric salts meet the requirements of the technical scheme of the invention.
As a preferable mode, the addition concentration of the ferrous salt in the wet desulfurization waste water is 0.3 to 0.8 times, more preferably 0.4 to 0.6 times, and most preferably 0.5 times the molar concentration of sulfite in the wet desulfurization waste water. The preferable ferrous salt addition concentration can ensure the full reaction with ammonia nitrogen and sulfite, and the ammonia nitrogen concentration is reduced to avoid the precipitation of magnesium ammonium chloride.
As a preferred embodiment, the concentration is achieved by a step evaporation concentration device.
As a preferable scheme, the concentration process adopts 3-level concentration treatment, and the concentration multiple is more than or equal to 14.
As a preferable scheme, the high-chlorine strong brine is diluted by steam condensate water generated in the evaporation process to obtain dilute salt low ammonia water so as to replace part of industrial water for recycling.
As a preferable scheme, the wet desulfurization wastewater itself presents acidity, and the pH value is further reduced after concentration, so that the pH value of the wet desulfurization wastewater is strictly controlled within the range of 6-9 in order to ensure that ferrous salts, sulfite and ammonia nitrogen are converted into ferrous ammonium sulfite with high selectivity, and the pH value of the concentrated wet desulfurization wastewater is ensured to be 5-8, so that the optimal pH range of ferrous salt precipitation ammonia nitrogen is ensured. The alkaline substance used for regulating pH is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
The mixing mode related by the invention is mechanical stirring, magnetic stirring or shaking table vibration.
According to the technical scheme, the conversion of ammonia nitrogen in the high-wet desulphurization wastewater is realized by adopting the magnesium ammonium phosphate method, the pH value of the wastewater solution is required to be ensured to be 8-10 during concentration by adopting the magnesium ammonium phosphate method, and meanwhile, phosphate radicals are added to enable ammonia nitrogen and magnesium ions in the wastewater to react with externally added phosphate radicals to form magnesium ammonium phosphate, so that the formation of magnesium ammonium chloride can be effectively prevented. However, the method has obvious defects that the pH condition for generating magnesium ammonium phosphate is strict, ammonia nitrogen is easily converted into free ammonia to enter the atmosphere to cause pollution under the high pH condition, and meanwhile, the introduction of phosphate radical introduced from the outside is easy to cause the water quality to exceed the standard, so that the subsequent high-chlorine strong brine is difficult to recycle. Therefore, the technical scheme of the invention adopts the ferrous ammonium sulfite method under milder conditions, does not introduce foreign ions, and has good inhibiting effect on the formation of magnesium ammonium chloride.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the technical scheme of the invention can effectively inhibit the formation of magnesium ammonium chloride and effectively reduce the chloride ion content in the recovered gypsum.
2. The invention has the advantages of few chemical medicine types, simple process and equipment and low energy consumption, and only needs alkaline substances and ferrous salt.
3. The method can simply, conveniently and quickly reduce the ammonia nitrogen concentration in the wet desulphurization wastewater, and avoid the problems of higher energy consumption, higher running cost and the like in the traditional treatment process. Belongs to the technical field of wet desulphurization wastewater treatment.
Drawings
FIG. 1 is a process flow diagram of a method of improving the purity of wet desulfurization wastewater by-products of the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
The wet desulfurization wastewater of the following examples and comparative examples mainly contained sulfate 2794mg/L, sulfite 1828mg/L, calcium ion 2338mg/L, ammonium ion 1450mg/L and chloride ion 19600mg/L.
Example 1
The method for controlling the purity of the wet desulfurization wastewater by-product in the embodiment comprises the following steps:
(1) Taking 5L of wet desulfurization wastewater, and adding sodium hydroxide to adjust the pH of the wastewater solution to 6.4;
(2) Adding 15.06g of ferrous sulfate into the wet desulphurization wastewater after the pH adjustment in the step (1), and uniformly stirring by a mechanical arm;
(3) Introducing steam into the steam side of a 3-stage evaporative concentration device;
(4) Introducing the wet desulfurization wastewater in the step (2) into the water side of a step evaporation concentration device;
(5) The wastewater in the step (4) is concentrated by 3 levels to obtain wastewater with high suspended matters;
(6) Introducing the high-suspended-matter wastewater in the step (5) into a plate-and-frame filter press for solid-liquid separation, wherein the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite, and the liquid is high-salt water;
(7) Drying the low-chlorine calcium sulfate and ferrous ammonium sulfite solid obtained in the step (6) to constant weight at 80 ℃ and recycling the solid;
(8) And (3) condensing the steam in the step (3) to generate condensed water, recovering the condensed water, introducing the condensed water into the high-salt water in the step (6), and diluting to obtain dilute-salt low-ammonia water so as to replace part of industrial water for recycling.
In example 1, the chlorine content of the obtained low-chlorine calcium sulfate and ferrous ammonium sulfite was 4.88% and the weight was 25.60g; the high-salt water contains 10920mg/L sulfate radical, 5250mg/L sulfite radical, 7338mg/L calcium ion, 3565mg/L ammonium ion, 239540mg/L chloride ion and the like.
Example 2
The method for controlling the purity of the wet desulfurization wastewater by-product in the embodiment comprises the following steps:
(1) Taking 5L of wet desulfurization wastewater, and adding sodium hydroxide to adjust the pH of the wastewater solution to 7.8;
(2) Adding 18.56g of ferrous sulfate into the wet desulphurization wastewater after the pH adjustment in the step (1), and uniformly stirring by a mechanical arm;
(3) Introducing steam into the steam side of a 3-stage evaporative concentration device;
(4) Introducing the wet desulfurization wastewater in the step (2) into the water side of a step evaporation concentration device;
(5) The wastewater in the step (4) is concentrated by 3 levels to obtain wastewater with high suspended matters;
(6) Introducing the high-suspended-matter wastewater in the step (5) into a plate-and-frame filter press for solid-liquid separation, wherein the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite, and the liquid is high-salt water;
(7) Drying the low-chlorine calcium sulfate and ferrous ammonium sulfite solid obtained in the step (6) to constant weight at 80 ℃ and recycling the solid;
(8) And (3) condensing the steam in the step (3) to generate condensed water, recovering the condensed water, introducing the condensed water into the high-salt water in the step (6), and diluting to obtain dilute-salt low-ammonia water so as to replace part of industrial water for recycling.
In example 2, the chlorine content of the obtained low-chlorine calcium sulfate and ferrous ammonium sulfite was 4.31% and the weight was 28.50g; the high-salt water contains 10876mg/L sulfate radical, 5350mg/L sulfite radical, 7340mg/L calcium ion, 3321mg/L ammonium ion, 245239mg/L chloride ion and the like.
Example 3
The method for controlling the purity of the wet desulfurization wastewater by-product in the embodiment comprises the following steps:
(1) Taking 5L of wet desulfurization wastewater, and adding sodium hydroxide to adjust the pH of the wastewater solution to 9.0;
(2) Adding 26.00g of ferrous sulfate into the wet desulphurization wastewater after the pH adjustment in the step (1), and uniformly stirring by a mechanical arm;
(3) Introducing steam into the steam side of a 3-stage evaporative concentration device;
(4) Introducing the wet desulfurization wastewater in the step (2) into the water side of a step evaporation concentration device;
(5) The wastewater in the step (4) is concentrated by 3 levels to obtain wastewater with high suspended matters;
(6) Introducing the high-suspended-matter wastewater in the step (5) into a plate-and-frame filter press for solid-liquid separation, wherein the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite, and the liquid is high-salt water;
(7) Drying the low-chlorine calcium sulfate and ferrous ammonium sulfite solid obtained in the step (6) to constant weight at 80 ℃ and recycling the solid;
(8) And (3) condensing the steam in the step (3) to generate condensed water, recovering the condensed water, introducing the condensed water into the high-salt water in the step (6), and diluting to obtain dilute-salt low-ammonia water so as to replace part of industrial water for recycling.
In example 3, the chlorine content of the obtained low-chlorine calcium sulfate and ferrous ammonium sulfite was 4.37%, the weight was 27.71g, and the chlorine content was 4.37%; the high-salt water contains 10997mg/L sulfate radical, 5298mg/L sulfite radical, 7471mg/L calcium ion, 3875mg/L ammonium ion, 242356mg/L chloride ion and the like.
Comparative example 1
The method for controlling the purity of the wet desulfurization wastewater by-product in the embodiment comprises the following steps:
(1) Taking 5L of wet desulfurization wastewater, and adding sodium hydroxide to adjust the pH of the wastewater solution to 3.0;
(2) Adding 32.00g of ferrous sulfate into the wet desulphurization wastewater after the pH adjustment in the step (1), and uniformly stirring by a mechanical arm;
(3) Introducing steam into the steam side of a 3-stage evaporative concentration device;
(4) Introducing the wet desulfurization wastewater in the step (2) into the water side of a step evaporation concentration device;
(5) The wastewater in the step (4) is concentrated by 3 levels to obtain wastewater with high suspended matters;
(6) Introducing the high-suspended-matter wastewater in the step (5) into a plate-and-frame filter press for solid-liquid separation, wherein the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite, and the liquid is high-salt water;
(7) Drying the low-chlorine calcium sulfate and ferrous ammonium sulfite solid obtained in the step (6) to constant weight at 80 ℃ and recycling the solid;
(8) And (3) condensing the steam in the step (3) to generate condensed water, recovering the condensed water, introducing the condensed water into the high-salt water in the step (6), and diluting to obtain dilute-salt low-ammonia water so as to replace part of industrial water for recycling.
In comparative example 1, chlorine content in the obtained low-chlorine calcium sulfate and ferrous ammonium sulfite was 31.73% and weight was 11.77g; the high-salt water contains 10857mg/L sulfate radical, 9558mg/L sulfite radical, 7290mg/L calcium ion, 12834mg/L ammonium ion, 178470mg/L chloride ion and the like.
Comparative example 2
The method for controlling the purity of the wet desulfurization wastewater by-product in the embodiment comprises the following steps:
(1) Taking 5L of wet desulfurization wastewater, and adding sodium hydroxide to adjust the pH of the wastewater solution to 10.0;
(2) Adding 7.50g of ferrous sulfate into the wet desulphurization wastewater after the pH adjustment in the step (1), and uniformly stirring by a mechanical arm;
(3) Introducing steam into the steam side of a 3-stage evaporative concentration device;
(4) Introducing the wet desulfurization wastewater in the step (2) into the water side of a step evaporation concentration device;
(5) The wastewater in the step (4) is concentrated by 3 levels to obtain wastewater with high suspended matters;
(6) Introducing the high-suspended-matter wastewater in the step (5) into a plate-and-frame filter press for solid-liquid separation, wherein the solid is low-chlorine calcium sulfate and ferrous ammonium sulfite, and the liquid is high-salt water;
(7) Drying the low-chlorine calcium sulfate and ferrous ammonium sulfite solid obtained in the step (6) to constant weight at 80 ℃ and recycling the solid;
(8) And (3) condensing the steam in the step (3) to generate condensed water, recovering the condensed water, introducing the condensed water into the high-salt water in the step (6), and diluting to obtain dilute-salt low-ammonia water so as to replace part of industrial water for recycling.
In comparative example 2, chlorine content in the obtained low-chlorine calcium sulfate and ferrous ammonium sulfite was 26.31% and weight was 13.41g; the high-salt water contains 10387mg/L sulfate, 10922mg/L sulfite, 7261mg/L calcium ion, 9934mg/L ammonium ion, 191640mg/L chloride ion and the like.
Claims (5)
1. A method for improving the purity of wet desulphurization waste water byproducts is characterized by comprising the following steps: adjusting the pH of the wet desulfurization wastewater to 6-9, and then mixing the wet desulfurization wastewater with ferrous salt for reaction to obtain a mixed solution; concentrating the mixed solution and separating solid from liquid, wherein the solid is a low-chlorine calcium sulfate and ferrous ammonium sulfite product, and the liquid is high-chlorine strong brine; the wet desulfurization wastewater contains 2100-3200 mg/L sulfate, 800-2000 mg/L sulfite, 2000-3100 mg/L calcium ion, 1000-2500 mg/L ammonium ion and 15000-20000 mg/L chloride ion.
2. A method for increasing the purity of wet desulfurization waste water by-products according to claim 1, wherein: the ferrous salt is at least one of ferrous sulfate heptahydrate, ferrous chloride tetrahydrate and ferrous nitrate.
3. A method for improving the purity of wet desulfurization waste water by-products according to claim 1 or 2, characterized in that: the addition concentration of the ferrous salt in the wet desulfurization wastewater is 0.3-0.8 times of the molar concentration of the sulfite in the wet desulfurization wastewater.
4. A method for increasing the purity of wet desulfurization waste water by-products according to claim 1, wherein: the concentration is achieved by a step evaporation concentration device.
5. The method for improving the purity of the wet desulfurization wastewater by-product according to claim 4, wherein: the concentration process adopts 3-level concentration treatment, and the concentration multiple is more than or equal to 14.
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| JPS51126990A (en) * | 1975-04-30 | 1976-11-05 | Idemitsu Kosan Co Ltd | Process for removing nitrogen oxides |
| KR100798417B1 (en) * | 2007-07-26 | 2008-01-28 | 한국지질자원연구원 | Preparation method of magnesium chloride anhydrate from magnesium chloride aqueous solution with ammonium chloride |
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| CN109354248A (en) * | 2018-11-12 | 2019-02-19 | 湘潭大学 | A kind of processing method of wet desulphurization waste water |
| CN111268753A (en) * | 2020-02-14 | 2020-06-12 | 北京光耀环境工程有限公司 | Desulfurization wastewater treatment system and method |
| CN111847701A (en) * | 2019-04-29 | 2020-10-30 | 中冶长天国际工程有限责任公司 | Pretreatment method of ultrahigh-concentration ammonia nitrogen wastewater |
| CN112299491A (en) * | 2019-07-30 | 2021-02-02 | 中冶长天国际工程有限责任公司 | Method for synthesizing ferrous ammonium sulfite |
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2021
- 2021-11-03 CN CN202111293158.9A patent/CN114212930B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126990A (en) * | 1975-04-30 | 1976-11-05 | Idemitsu Kosan Co Ltd | Process for removing nitrogen oxides |
| KR100798417B1 (en) * | 2007-07-26 | 2008-01-28 | 한국지질자원연구원 | Preparation method of magnesium chloride anhydrate from magnesium chloride aqueous solution with ammonium chloride |
| CN107098372A (en) * | 2017-04-19 | 2017-08-29 | 湖北三宁化工股份有限公司 | A kind of method that hydrochloric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide |
| CN109354248A (en) * | 2018-11-12 | 2019-02-19 | 湘潭大学 | A kind of processing method of wet desulphurization waste water |
| CN111847701A (en) * | 2019-04-29 | 2020-10-30 | 中冶长天国际工程有限责任公司 | Pretreatment method of ultrahigh-concentration ammonia nitrogen wastewater |
| CN112299491A (en) * | 2019-07-30 | 2021-02-02 | 中冶长天国际工程有限责任公司 | Method for synthesizing ferrous ammonium sulfite |
| CN111268753A (en) * | 2020-02-14 | 2020-06-12 | 北京光耀环境工程有限公司 | Desulfurization wastewater treatment system and method |
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