CN113321226A - Method for removing fluorine in ionic membrane caustic soda by using brine prepared from chlorination residues - Google Patents
Method for removing fluorine in ionic membrane caustic soda by using brine prepared from chlorination residues Download PDFInfo
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- CN113321226A CN113321226A CN202110733981.0A CN202110733981A CN113321226A CN 113321226 A CN113321226 A CN 113321226A CN 202110733981 A CN202110733981 A CN 202110733981A CN 113321226 A CN113321226 A CN 113321226A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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Abstract
The method relates to a method for removing fluorine in brine prepared from chlorination residues and used for ionic membrane caustic soda, which comprises the following steps: a. adding tap water into the chlorination residues according to the slag-water ratio of 1.0: 1.0-2.0, stirring, and filtering to obtain filtrate; b. adding alkali liquor into the filtrate, wherein the volume ratio of the filtrate to the alkali liquor is 1.0: 0.6-0.8, and stirring; c. rapidly adding a sodium hypochlorite solution into the mixed solution, wherein the volume ratio of the mixed solution to the sodium hypochlorite solution is 1.0: 0.4-0.8, stirring at 500-800 rpm, and stirring for 30-60 min; d. and standing the solution for 48-72 h, and filtering to obtain brine. The method prepares the crude brine by water quenching of the waste chlorination residues, and eliminates the influence of fluorine ions in the crude brine on ionic membrane caustic soda by a process technology for removing iron and manganese from the crude brine at the same time, thereby providing guarantee for resource utilization of the waste chlorination residues. Solves the problems of complex procedures and high cost of the existing chlorination waste residue water treatment.
Description
Technical Field
The invention relates to a method for removing fluorine in brine prepared from chlorination residues and used for ionic membrane caustic soda, belonging to the technical field of recycling of the chlorination residues.
Background
The vanadium-titanium resources in Panxi areas are rich, wherein the titanium reserves account for about 90 percent of the total amount of the titanium resources in China. In order to fully develop Panxi titanium resources, Panxi steel adopts a more advanced molten salt chlorination method to produce TiCl4The process has the characteristics of low production cost and high product quality, but also has the problems of high yield of waste salt (quasi-hazardous waste) and waste brine (hazardous waste) and serious pollution, and seriously restricts the popularization of the molten salt chlorination technology and the application of primary titanium ore. Meanwhile, the composition of a large amount of chlorination residue waste brine generated by the process for extracting titanium from blast furnace slag is similar to that of molten salt chlorination waste brine, and the pollution to the environment is serious.
Therefore, a whole set of wastewater treatment process is independently developed in Panzhihua steel, ions such as Fe, Mn and Mg in wastewater are recycled step by step, and finally the waste salt water is used for preparing chlorine and caustic soda by an ion membrane caustic soda process, so that the full resource utilization of the waste salt and the chlorination residues in the molten salt chlorination is realized. However, in practice, the fluorine ion content is too high, and the fluorine ion penetrates through the ionic membrane and enters cathode water, so that the electrode is corroded, and the service life of the electrode is shortened.
An electric flocculation and pipe type microfiltration coupling high-concentration brine deep fluorine removal device with the application number of 202011149758.3 provides an electric flocculation fluorine removal method for high-concentration brine. And the aim of removing fluorine is achieved by methods such as polymeric ferric sulfate, modified zeolite, ion exchange and the like commonly used in the electrolytic zinc industry. However, in actual operation, the cost and power consumption of equipment are found to be high, which results in high production cost and is not suitable for waste liquid recovery projects.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method for treating the waste chlorinated slag water is complex in process, high in cost and incapable of being recycled.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda comprises the following steps:
a. adding tap water into the chlorination residue according to the slag-water ratio of 1.0: 1.0-2.0, stirring at 500-800 rpm for 10-30 min, and filtering and separating after the reaction is finished to obtain filtrate;
b. adding alkali liquor into the filtrate, wherein the volume ratio of the filtrate to the alkali liquor is 1.0: 0.6-0.8, and stirring at 500-800 rpm;
c. rapidly adding a sodium hypochlorite solution into the mixed solution, wherein the volume ratio of the mixed solution to the sodium hypochlorite solution is 1.0: 0.4-0.8, stirring at 500-800 rpm, and stirring for 30-60 min;
d. and standing the solution for 48-72 h, and filtering to obtain brine.
Wherein the chlorination residue in the step a in the method is waste salt or chlorination residue of molten salt chlorination.
Wherein the alkali liquor in the step b in the method is 8 to 12 percent sodium carbonate saturated solution of sodium hydroxide.
Wherein the Fe content in the filtrate is determined in step c of the method2+Concentration, in terms of Fe2+:ClO-Sodium hypochlorite solution was added at a ratio of 2.0: 1.0-1.2.
Wherein the available chlorine in the sodium hypochlorite solution in the step c in the method is 14-28 g/l.
Wherein the mixed alkali and sodium hypochlorite in the steps b and c in the method are industrial waste alkali liquor or waste brine with the pH value of about 9-13.
The invention has the beneficial effects that: the process comprises the steps of preparing crude brine by water quenching of chlorination residues, removing iron and manganese from the crude brine at the same time, reducing the fluorine content in the waste brine to meet the standard requirement of qualified brine (less than 0.5mg/l), further removing impurities from the treated brine for ionic membrane caustic soda, and using a ferric hydroxide mixture as a sintering raw material or other alloy production raw materials. The process eliminates the influence of fluorine ions in the crude brine on the ionic membrane caustic soda, is simple, convenient and easy to realize, and provides guarantee for resource utilization of the waste chlorination residues. The method can be used for an ionic membrane caustic soda process through further impurity removal, realizes resource treatment of the waste chlorination residues, has good economic benefit, has great significance for eliminating the bottleneck of application and development of molten salt chlorination and titanium extraction from blast furnace slag, can obviously improve the market competitiveness of titanium white chloride and titanium sponge enterprises, and has wide market prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
The invention relates to a method for removing fluorine in brine prepared from chlorination residues and used for ionic membrane caustic soda, which comprises the following steps:
a. adding tap water into the chlorination residue according to the slag-water ratio of 1.0: 1.0-2.0, stirring at 500-800 rpm for 10-30 min, and filtering and separating after the reaction is finished to obtain filtrate;
b. adding alkali liquor into the filtrate, wherein the volume ratio of the filtrate to the alkali liquor is 1.0: 0.6-0.8, and stirring at 500-800 rpm;
c. rapidly adding a sodium hypochlorite solution into the mixed solution, wherein the volume ratio of the mixed solution to the sodium hypochlorite solution is 1.0: 0.4-0.8, stirring at 500-800 rpm, and stirring for 30-60 min;
d. and standing the solution for 48-72 h, and filtering to obtain brine. As will be appreciated by those skilled in the art, the present process oxidizes Fe by hypochlorite primarily through precipitation of Fe, Mn, Mg, etc. ions2+The purpose of (1). At the same time, a small amount of Fe in the filtrate3+And F-Possibly forming FeF6 3And stable, with increasing system pH and Fe2+Is oxidized to release F-Reacting it with part of Ca2+Reaction to form CaF2Precipitation with Fe (OH)3The purpose of defluorination can be achieved by the wrapping and flocculation of the colloid.
Preferably, the chlorination residue in the step a in the method is waste salt or chlorination residue of molten salt chlorination. As can be understood by those skilled in the art, the method is only used for preferably selecting the source of the chlorination residues, and realizes the composition of a large amount of chlorination residue waste brine generated in the titanium extraction process from the Fuco slag and the effective recovery and treatment of the molten salt chlorination waste, thereby reducing pollution.
Preferably, the alkali liquor in step b of the method is 8% -12% sodium carbonate saturated solution of sodium hydroxide. As will be appreciated by those skilled in the art, the lye of the process is primarily an increase in pH which maintains the overall mixture in an alkaline environment while allowing the major portion of the manganese to precipitate and a minor portion of the ferrous and magnesium to precipitate. In practical consideration of economy, reaction effect and convenience in field operation, a saturated sodium carbonate solution is preferred, and a saturated sodium carbonate solution with 8% -12% of sodium hydroxide as an alkali solution is further preferred.
Preferably, the method is such that in step c the filtrate is Fe2+Concentration, in terms of Fe2+:ClO-Sodium hypochlorite solution was added at a ratio of 2.0: 1.0-1.2. It will be appreciated by those skilled in the art that Fe is added to ensure sodium hypochlorite is added2+Total oxidation to Fe3+,Preferably, the hypochlorite solution contains more hypochlorite than Fe2+Therefore, the method is preferably performed according to Fe2+:ClO-Sodium hypochlorite solution was added at a ratio of 2.0: 1.0-1.2.
Preferably, in the method, the available chlorine in the sodium hypochlorite solution in the step c is 14-28 g/l. As can be understood by those skilled in the art, in order to ensure the oxidation effect of the sodium hypochlorite solution, the effective chlorine in the sodium hypochlorite solution is preferably 14-28 g/l.
Preferably, the alkali mixture and sodium hypochlorite in steps b and c in the method are industrial waste lye or waste brine with the pH value of about 9-13. The technical personnel in the field can understand that, in order to reduce the cost and simultaneously realize the purpose of treating wastes with wastes, the mixed alkali and sodium hypochlorite used in practice are waste alkali liquids generated in other working sections in a plant, wherein the mixed alkali and the sodium hypochlorite contain sodium carbonate, sodium hypochlorite and the like, and the pH value is ensured to meet 9-13.
Example 1
(1) 1kg of fused salt chlorination slag is taken and added into 2L of tap water to be stirred and dissolved. And filtering after the molten salt chlorination residues are completely dissolved to obtain 1.85L of crude brine. The composition and content of the crude brine are shown in Table 1-1. Wherein the content of fluorine ions is 20 mg/l.
TABLE 1-1 crude brine composition (g/l)
pH | Na+ | Fe2+ | Mg2+ | Mn2+ | Ca2+ | Al3+ | Ti | F |
1.08 | 40.40 | 29.00 | 24.10 | 4.91 | 2.31 | 0.31 | 0.004 | 0.02 |
(2) While stirring, 1.3L of a saturated solution of sodium carbonate containing 10% sodium hydroxide at 30 ℃ was slowly added, and stirring was continued at 800 rpm.
(3) Adding 1.2L sodium hypochlorite solution with effective chlorine content of 14.5g/L into the solution, stirring at 800rpm for 40min, standing for 48h, and filtering to obtain qualified saline water, wherein the components of the qualified saline water are shown in Table 1-2. Qualified Fe in brine2+、Mn2+The content of the fluorine ions is less than 0.2mg/l while the content of the fluorine ions is less than 1 mg/l.
TABLE 1-2 quality brine composition (g/l)
Na+ | Fe2+ | Mg2+ | Mn2+ | Ca2+ | Al3+ | Ti | F |
62.5 | <0.001 | 13.55 | <0.001 | 0.07 | <0.001 | <0.001 | <0.0002 |
Example 2
(1) 1kg of chlorination residue was taken, and 1.2L of tap water was added thereto, and stirred at 800rpm for 20 min. The solution was filtered to give 0.91L of tailings wash water (crude brine). The composition and content of the crude brine are shown in Table 2-1. Wherein the content of fluorine ions is 100 mg/l.
TABLE 2-1 crude brine composition (g/l)
pH | Na+ | Fe2+ | Mg2+ | Mn2+ | Ca2+ | Al3+ | Ti | F |
3.2 | 0.61 | 7.10 | 2.31 | 1.01 | 15.4 | 0.07 | <0.001 | 0.10 |
(2) While stirring, 0.59L of a saturated solution of sodium carbonate containing 10% sodium hydroxide was slowly added, and stirring was continued at 800 rpm.
(3) Adding sodium hypochlorite solution 0.4L with effective chlorine content of 10.01g/L into the solution, stirring at 500rpm for 30min, standing for 72 hr, and filtering to obtain qualified salt water with the components shown in Table2-2. Qualified Fe in brine2+、Mn2+The content of the fluorine ions is less than 0.2mg/l while the content of the fluorine ions is less than 1 mg/l.
TABLE 2-2 quality brine composition (g/l)
Fe2+ | Mg2+ | Mn2+ | Ca2+ | Al3+ | Ti | F |
<0.001 | 2.23 | <0.001 | 0.02 | <0.001 | <0.001 | <0.0002 |
In conclusion, the brine Fe2+, Mn2+, fluoride ions and the like finally prepared by the method all meet the requirements of the ionic membrane caustic soda process on the brine, and the waste brine is finally used for preparing chlorine and caustic soda by the ionic membrane caustic soda process, so that the full resource utilization of the waste salt and the chlorination residues of the molten salt chlorination is realized.
Claims (6)
1. The method for removing fluorine from brine prepared from waste chlorination residues for ionic membrane caustic soda is characterized by comprising the following steps:
a. adding tap water into the chlorination residue according to the slag-water ratio of 1.0: 1.0-2.0, stirring at 500-800 rpm for 10-30 min, and filtering and separating after the reaction is finished to obtain filtrate;
b. adding alkali liquor into the filtrate, wherein the volume ratio of the filtrate to the alkali liquor is 1.0: 0.6-0.8, and stirring at 500-800 rpm;
c. rapidly adding a sodium hypochlorite solution into the mixed solution, wherein the volume ratio of the mixed solution to the sodium hypochlorite solution is 1.0: 0.4-0.8, stirring at 500-800 rpm, and stirring for 30-60 min;
d. and standing the solution for 48-72 h, and filtering to obtain brine.
2. The method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda according to claim 1, which is characterized in that: the chlorination residue in the step a is molten salt chlorination waste salt or chlorination residue.
3. The method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda according to claim 1, which is characterized in that: and in the step b, the alkali liquor is a sodium carbonate saturated solution of 8-12% of sodium hydroxide.
4. The method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda according to claim 1, which is characterized in that: according to Fe in filtrate in step c2+Concentration, in terms of Fe2+:ClO-Sodium hypochlorite solution was added at a ratio of 2.0: 1.0-1.2.
5. The method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda according to claim 1, which is characterized in that: in the step c, the available chlorine in the sodium hypochlorite solution is 14-28 g/l.
6. The method for removing fluorine in brine prepared from waste chlorination residues and used for ionic membrane caustic soda according to claim 1, which is characterized in that: the mixed alkali and the sodium hypochlorite in the steps b and c are industrial waste alkali liquor or waste brine with the pH value of about 9-13.
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