CN116216785A - Method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag - Google Patents

Method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag Download PDF

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Publication number
CN116216785A
CN116216785A CN202310038218.5A CN202310038218A CN116216785A CN 116216785 A CN116216785 A CN 116216785A CN 202310038218 A CN202310038218 A CN 202310038218A CN 116216785 A CN116216785 A CN 116216785A
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ferrous
waste acid
molten salt
stirring
crystals
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李建军
张伟
陈建立
黄海广
祝永红
李鑫洋
张军丽
金蓓
赵杰涛
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Yunnan Guoti Metal Co ltd
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Yunnan Guoti Metal Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/10Halides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for leaching and purifying ferrous chloride by using chloridized waste acid and fused salt slag, which comprises the following steps of 1) mixing and dissolving fused salt slag and titanium white waste acid, and adding polyacrylamide to obtain saturated ferrous liquid; 2) Adding the saturated ferrous liquid into a crystallization tank, stirring, cooling and filtering to obtain mother crystals; 3) Dissolving mother crystal in pure water to prepare solution, adding alkali to adjust pH to 3.5, adding phosphorus salt, and filtering by a diatomite-loaded filter device; 4) Introducing HCl gas into the filtrate, stirring, cooling, and filtering to obtain purified ferrous crystals; 5) Adding purified ferrous crystals into purified water at 80 ℃ to prepare a solution, adding the solution into a crystallization tank, stirring, cooling, centrifuging and filtering to obtain ferrous chloride crystals. The invention enables FeCl to be obtained 2 Can be separated from a solid-liquid system with a plurality of impurities to generate value; the property of solid dangerous wastes of molten salt slag is changed, the problems of difficult resource recovery, high environmental protection pressure and the like are solved, and the sustainable development capability of enterprises is improved.

Description

Method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag
Technical Field
The invention relates to the technical field of purification, in particular to a method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag.
Background
Titanium tetrachloride is an important intermediate product for producing titanium dioxide and titanium sponge, and the main waste and side outlets of the molten salt chlorination method and the boiling chlorination method are respectively chlorinated waste acid after pulping of molten salt slag and dust collection slag. NaCl and FeCl as main components in molten salt slag 2 、MgCl 2 、CaCl 2 Mineral coke and the like, mixing lime after cooling and crushing, and neutralizing and stacking; feCl as main component in chloridizing waste acid 2 、MgCl 2 、AlCl 3 、MnCl 2 And the like, neutralizing the mixture into hydroxide slag by adding alkali, and stacking the hydroxide slag; both methods cannot realize resource utilization and have high environmental protection pressure.
The two substances which are high in waste side amount and are shared are FeCl 2 While FeCl in general 2 The production mode is mainly an evaporation crystallization method with high energy consumption, and FeCl is extracted from chlorinated waste acid and molten salt slag 2 At present, no effective separation and purification means exist.
Disclosure of Invention
The invention provides a method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag, which aims to solve the problems in the prior art.
The scheme of the invention is as follows:
a method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag comprises the following steps:
1) Mixing molten salt slag and titanium white waste acid according to the mass ratio of 0.8-1.5:1, stirring and dissolving until Fe in the solution 2+ Adding polyacrylamide with the mass fraction of 0.5% when the concentration reaches 140-160 g/L, and filtering while the mixture is hot after flocculation to obtain saturated ferrous liquid;
2) Adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain mother crystals;
3) The mother crystal is dissolved in pure water to prepare Fe 2+ Adding alkali into 100-130 g/L solution to adjust the pH to 3.5, adding 0.5-0.8% of phosphorus salt by mass percent, and filtering by a diatomite-loaded filter device;
4) Introducing HCl gas into the filtered liquid, pumping into a crystallization tank when the acidity reaches 21-25%, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain purified ferrous crystals;
5) Adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 240-260 g/L solution is pumped into a crystallization tank, stirred and cooled to 0 ℃ at a speed of 150-200 r/min, and centrifugally filtered to obtain ferrous chloride crystals with uniform particles and purity of 98 percent.
As a preferable technical characteristic, the molten salt slag and the titanium white waste acid in the step 1) are mixed according to a mass ratio of 1:1 for stirring and dissolving.
As a preferred feature, the crystallization pot in step 2) is stirred at a rate of 180 revolutions per minute.
As a preferable technical feature, the mother crystal in the step 3) is dissolved in pure water to be prepared into Fe 2+ 120g/L concentration.
As a preferable technical feature, the step 4) is carried out by stirring the mixture at a speed of 180 revolutions per minute after the acidity reaches 25%.
As a preferable technical feature, purified ferrous crystals are added with purified water at 80 ℃ to be dissolved and prepared into Fe 2+ 250g/L solution.
As a preferable technical feature, the mixture is poured into a crystallization tank and stirred at a speed of 180 revolutions per minute.
The method for leaching and purifying ferrous chloride by using the chloridized waste acid and the fused salt slag through the technical scheme comprises the following steps of 1) mixing the fused salt slag and the titanium white waste acid according to the mass ratio of 0.8-1.5:1, stirring and dissolving, and waiting for Fe in the solution 2+ Adding polyacrylamide with the mass fraction of 0.5% when the concentration reaches 140-160 g/L, and filtering while the mixture is hot after flocculation to obtain saturated ferrous liquid; 2) Adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at the speed of 150-200 rpm for preservingStanding for 30min, and filtering to obtain mother crystal; 3) The mother crystal is dissolved in pure water to prepare Fe 2+ Adding alkali into 100-130 g/L solution to adjust the pH to 3.5, adding 0.5-0.8% of phosphorus salt by mass percent, and filtering by a diatomite-loaded filter device; 4) Introducing HCl gas into the filtered liquid, pumping into a crystallization tank when the acidity reaches 21-25%, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain purified ferrous crystals; 5) Adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 240-260 g/L solution is pumped into a crystallization tank, stirred and cooled to 0 ℃ at a speed of 150-200 r/min, and centrifugally filtered to obtain ferrous chloride crystals with uniform particles and purity of 98 percent.
The invention has the advantages that:
the invention uses the FeCl in the chloridized waste acid and fused salt slag 2 The superposition of the contents reaches a supersaturation state to separate out crystals, and then flocculant and filter aid are added to remove tiny solid impurities, and pH is adjusted to precipitate Al, V and Fe 3+ Purifying Si and the like by a diatomite-loaded filter device, and finally purifying by recrystallization;
the method can realize Fe in double wastes 2+ The combination leaching of the molten salt slag and the solid dangerous waste property are changed, and the Fe is skillfully utilized 2+ In the dissolution balance of a complex acid water system, fe is introduced into a HCl gas way 2+ The unsaturated state is changed into a supersaturated state, so that the problem of high energy consumption caused by traditional evaporation and crystallization is avoided, and the prepared ferrous chloride crystal has uniform particles, high purity, reduced waste side amount and resource utilization.
So that FeCl 2 Can be separated from a solid-liquid system with a plurality of impurities to generate value; the property of solid dangerous wastes of molten salt slag is changed, the problems of difficult resource recovery, high environmental protection pressure and the like are solved, and the sustainable development capability of enterprises is improved.
Detailed Description
In order to overcome the defects, the invention provides a method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag, which solves the problems in the background technology.
A method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag comprises the following steps:
1) Mixing molten salt slag and titanium white waste acid according to the mass ratio of 0.8-1.5:1, stirring and dissolving until Fe in the solution 2+ Adding polyacrylamide with the mass fraction of 0.5% when the concentration reaches 140-160 g/L, and filtering while the mixture is hot after flocculation to obtain saturated ferrous liquid;
2) Adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain mother crystals;
3) The mother crystal is dissolved in pure water to prepare Fe 2+ Adding alkali into 100-130 g/L solution to adjust the pH to 3.5, adding 0.5-0.8% of phosphorus salt by mass percent, and filtering by a diatomite-loaded filter device;
4) Introducing HCl gas into the filtered liquid, pumping into a crystallization tank when the acidity reaches 21-25%, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain purified ferrous crystals;
5) Adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 240-260 g/L solution is pumped into a crystallization tank, stirred and cooled to 0 ℃ at a speed of 150-200 r/min, and centrifugally filtered to obtain ferrous chloride crystals with uniform particles and purity of 98 percent.
And in the step 1), mixing the molten salt slag and the titanium white waste acid according to the mass ratio of 1:1, and stirring and dissolving.
The crystallization pot in step 2) is stirred at a rate of 180 revolutions per minute.
The mother crystal in the step 3) is dissolved in pure water to be prepared into Fe 2+ 120g/L concentration.
And (3) when the acidity reaches 25%, pouring the mixture into a crystallization tank and stirring the mixture at a speed of 180 revolutions per minute.
Adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 250g/L solution.
Pouring into a crystallization tank and stirring at a speed of 180 revolutions per minute.
The invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1:
(1) stirring and dissolving molten salt slag and titanium white waste acid according to the mass ratio of 0.8:1, and waiting for Fe in the solution 2+ Adding PAM with the mass fraction of 0.5% when the concentration reaches 140g/L, and filtering while the mixture is hot after flocculation to obtain saturated ferrous liquid;
(2) adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 150/min, maintaining for 30min, and filtering to obtain mother crystals;
(3) dissolving the mother crystal in pure water to prepare a solution with concentration of Fe2+100g/L, adding alkali to adjust the pH to 3.5, adding 0.5 mass percent of phosphorus salt, and introducing the solution into a diatomite-loaded filter device for filtering;
(4) introducing fresh HCl gas into the filtrate, pouring into a crystallization tank when the acidity reaches 21%, stirring and cooling to 0 ℃ at a speed of 150 revolutions per minute, maintaining for 30min, and filtering to obtain purified ferrous crystals;
(5) adding purified ferrous crystals into purified water at 80 ℃ to dissolve and prepare Fe2+240g/L solution, pouring the solution into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 150 revolutions per minute, maintaining the temperature for 30min, and centrifugally filtering to obtain ferrous chloride crystals with uniform particles and purity of 98%.
Example 2
(1) Stirring and dissolving molten salt slag and titanium white waste acid according to a mass ratio of 1:1, adding PAM with a mass fraction of 0.5% when Fe < 2+ > in the solution reaches 150g/L, and filtering while the solution is hot after flocculation to obtain saturated ferrous liquid;
(2) adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 180 revolutions per minute, maintaining for 30min, and filtering to obtain mother crystals;
(3) dissolving the mother crystal in pure water to prepare a solution with concentration of Fe < 2+ > 120g/L, adding alkali to adjust the pH to 3.5, adding 0.8 mass percent of phosphorus salt, and introducing the solution into a diatomite-loaded filter device for filtering;
(4) introducing fresh HCl gas into the filtrate, pouring into a crystallization tank when the acidity reaches 25%, stirring and cooling to 0 ℃ at a speed of 180 revolutions per minute, maintaining for 30min, and filtering to obtain purified ferrous crystals;
(5) adding purified ferrous crystals into purified water at 80 ℃ to dissolve and prepare Fe2+250g/L solution, pouring the solution into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 180 revolutions per minute, maintaining the temperature for 30min, and centrifugally filtering to obtain ferrous chloride crystals with uniform particles and purity of 98%.
Example 3
(1) Stirring and dissolving molten salt slag and titanium white waste acid according to a mass ratio of 1.5:1, adding PAM with a mass fraction of 0.5% when Fe < 2+ > in the solution reaches 160g/L, flocculating, and filtering while the solution is hot to obtain saturated ferrous liquid;
(2) adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at the speed of 200 revolutions per minute, maintaining for 30min, and filtering to obtain mother crystals;
(3) dissolving the mother crystal in pure water to prepare a solution with concentration of Fe2+130g/L, adding alkali to adjust the pH to 3.5, adding 0.8 mass percent of phosphorus salt, and introducing the solution into a diatomite-loaded filter device for filtering;
(4) introducing fresh HCl gas into the filtrate, pouring into a crystallization tank when the acidity reaches 25%, stirring and cooling to 0 ℃ at a speed of 200 revolutions per minute, maintaining for 30min, and filtering to obtain purified ferrous crystals;
(5) adding purified ferrous crystals into purified water at 80 ℃ to dissolve and prepare Fe2+260g/L solution, pouring the solution into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 200 revolutions per minute, maintaining the temperature for 30min, and centrifugally filtering to obtain ferrous chloride crystals with uniform particles and purity of 98%.
The foregoing has shown and described the basic principles, main features and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. The method for leaching and purifying ferrous chloride by using the chlorinated waste acid and molten salt slag is characterized by comprising the following steps:
1) Mixing molten salt slag and titanium white waste acid according to the mass ratio of 0.8-1.5:1, stirring and dissolving until Fe in the solution 2+ Adding polyacrylamide with the mass fraction of 0.5% when the concentration reaches 140-160 g/L, flocculating, and filtering while the mixture is hot to obtain a saturated solutionAnd a ferrous liquid;
2) Adding saturated ferrous liquid into a crystallization tank, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain mother crystals;
3) The mother crystal is dissolved in pure water to prepare Fe 2+ Adding alkali into 100-130 g/L solution to adjust the pH to 3.5, adding 0.5-0.8% of phosphorus salt by mass percent, and filtering by a diatomite-loaded filter device;
4) Introducing HCl gas into the filtered liquid, pumping into a crystallization tank when the acidity reaches 21-25%, stirring and cooling to 0 ℃ at a speed of 150-200 rpm, maintaining for 30min, and filtering to obtain purified ferrous crystals;
5) Adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 240-260 g/L solution is pumped into a crystallization tank, stirred and cooled to 0 ℃ at a speed of 150-200 r/min, and centrifugally filtered to obtain ferrous chloride crystals with uniform particles and purity of 98 percent.
2. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: and in the step 1), mixing the molten salt slag and the titanium white waste acid according to the mass ratio of 1:1, and stirring and dissolving.
3. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: the crystallization pot in step 2) is stirred at a rate of 180 revolutions per minute.
4. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: the mother crystal in the step 3) is dissolved in pure water to be prepared into Fe 2+ 120g/L concentration.
5. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: and (3) when the acidity reaches 25%, pouring the mixture into a crystallization tank and stirring the mixture at a speed of 180 revolutions per minute.
6. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: adding purified water at 80 ℃ into purified ferrous crystals to dissolve and prepare Fe 2+ 250g/L solution.
7. The method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag according to claim 1, which is characterized in that: pouring into a crystallization tank and stirring at a speed of 180 revolutions per minute.
CN202310038218.5A 2023-01-09 2023-01-09 Method for leaching and purifying ferrous chloride by using chlorinated waste acid and molten salt slag Pending CN116216785A (en)

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Publication number Priority date Publication date Assignee Title
US5248497A (en) * 1991-09-17 1993-09-28 Kronos, Inc. Production of purified iron chloride by a vacuum process in the manufacture of titanium dioxide
CN105883930A (en) * 2016-05-26 2016-08-24 宜宾天原集团股份有限公司 Production process for preparing iron red from chlorination process titanium dioxide byproduct chloride residues
CN110980833A (en) * 2019-12-16 2020-04-10 斯瑞尔环境科技股份有限公司 Preparation method of electronic-grade ferrous chloride
CN113582224A (en) * 2021-09-06 2021-11-02 攀钢集团攀枝花钢铁研究院有限公司 Resource utilization method for titanium white waste acid leaching fused salt chlorination slag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248497A (en) * 1991-09-17 1993-09-28 Kronos, Inc. Production of purified iron chloride by a vacuum process in the manufacture of titanium dioxide
CN105883930A (en) * 2016-05-26 2016-08-24 宜宾天原集团股份有限公司 Production process for preparing iron red from chlorination process titanium dioxide byproduct chloride residues
CN110980833A (en) * 2019-12-16 2020-04-10 斯瑞尔环境科技股份有限公司 Preparation method of electronic-grade ferrous chloride
CN113582224A (en) * 2021-09-06 2021-11-02 攀钢集团攀枝花钢铁研究院有限公司 Resource utilization method for titanium white waste acid leaching fused salt chlorination slag

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Title
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