CN101898770B - Method for recycling sodium hydroxide - Google Patents
Method for recycling sodium hydroxide Download PDFInfo
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- CN101898770B CN101898770B CN2010101909028A CN201010190902A CN101898770B CN 101898770 B CN101898770 B CN 101898770B CN 2010101909028 A CN2010101909028 A CN 2010101909028A CN 201010190902 A CN201010190902 A CN 201010190902A CN 101898770 B CN101898770 B CN 101898770B
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- sodium
- solution
- sodium hydroxide
- sodium bicarbonate
- sulfate
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Abstract
The invention provides a method for recycling sodium hydroxide, which is mainly used for recycling used sodium hydroxide in a metallurgic and chemical technical process. The method comprises the following steps: adding calcium carbonate into a sodium sulfate solution, introducing carbon dioxide or adding sulfuric acid to regulate the pH value of the solution to ensure that the sodium sulfate is converted into sodium bicarbonate; filtering the sodium bicarbonate to obtain gypsum and a sodium bicarbonate solution; adding lime into the sodium bicarbonate solution for causticizing; filtering to obtain a regenerated sodium hydroxide solution and calcium carbonate; and returning the calcium carbonate to a sulfate sodium transition process for continuous use. The method has the advantages of simple process, convenient operation, economy, environmental protection and the like.
Description
Technical field
The present invention relates to method for recycling sodium hydroxide in a kind of industrial practice.
Background technology
Sodium hydroxide is one of common chemical reagent, it is widely used in chemical industry and metallurgy industry, and normally with the sulfuric acid use of going with, promptly successively add sulfuric acid and sodium hydroxide to satisfy the needs of technological process in technological process, no matter be what situation, the product of sulfuric acid and sodium hydroxide effect all is a sodium sulfate salt.The method that sodium sulfate salt regeneration sodium hydroxide is commonly used is hydrated barta displacement or Bipolar Membrane electrolysis.Sodium sulfate salt hydrated barta displacement regeneration obtains the sodium hydroxide possible in theory, but uneconomical economically, and hydrated barta is dangerous dangerous product.At present the PREPARATIOM OF BIPOLAR MEMBRANE technology does not also pass a test, the sodium hydroxide cost height that obtains of sodium sulfate salt regeneration not only, and also it is also bad to reclaim the quality of the sodium hydroxide that obtains.Though sodium sulfate salt is a kind of industrial chemicals commonly used, but its price is low, cost recovery is high, and the solubility with temperature of sodium sulfate salt in the aqueous solution alters a great deal, blocking pipe is separated out in crystallization easily, for medium and small sized enterprises, the trade effluent of sulfur acid sodium salt is directly discharging normally, causes environmental pollution.As seen, cost is the factor that enterprise pays special attention to, and how to accomplish both to have helped environmental protection, economizes on resources again, and the method that reduces cost is that existing technician is badly in need of solving, and a major issue of puzzlement enterprise.
Summary of the invention
The object of the present invention is to provide the method for recycling sodium hydroxide of the low and environmental protection of a kind of industrial feasible cost; this method not only helps applying of chemical industry, smelter; also can avoid because sodium hydroxide uses back discharging sodium sulfate salt waste water, protection environment.
Technical scheme of the present invention may further comprise the steps:
(1) in the mixing solutions of metabisulfite solution or sodium bisulfate or sodium sulfate and sodium pyrosulfate, extraordinarily goes into the calcium carbonate powders of particle diameter earlier less than 380 μ m by forming sodium bicarbonate chemical reaction stoichiometric number 1.0-3.0, and the pH value 3.0-9.0 of feeding carbonic acid gas or adding sulfuric acid regulation solution, behind the stirring reaction, filter and obtain gypsum and sodium hydrogen carbonate solution;
(2) and then by sodium bicarbonate causticization chemical reaction stoichiometric number 1.0-3.5 in the solution extraordinarily go into calcium oxide or calcium hydroxide, carry out causticizing reaction, filter and obtain lime carbonate and regeneration sodium hydroxide solution, lime carbonate returns in (1) step and continues to use.
The sodium hydroxide solution that regeneration obtains directly returns required technological cycle and uses, or returns required technological cycle with the form of soda-lye or sodium hydrate solid after concentrating and use.
In described (1) step, stirring reaction is to stir 0.5-4.5 hour at 0-60 ℃,
The condition of causticizing reaction is 0-110 ℃ of stirring 1-3 hour in described (2) step.
The reaction formula of technological process of the present invention is:
2NaOH+H
2SO
4＝Na
2SO
4+2H
2O
NaOH+H
2SO
4＝NaHSO
4+H
2O
Na
2SO
4+H
2SO
4+2CaCO
3+4H
2O＝2CaSO
4·2H
2O↓+2NaHCO
3
Na
2SO
4+CO
2+CaCO
3+4H
2O＝CaSO
4·2H
2O↓+2NaHCO
3
NaHSO
4+CaCO
3+2H
2O＝CaSO
4·2H
2O↓+NaHCO
3
2NaHCO
3+2Ca(OH)
2＝2CaCO
3↓+2NaOH+2H
2O
2NaHCO
3+2CaO＝2CaCO
3↓+2NaOH
Advantage of the present invention just is, the contriver is bridge cleverly with the sodium bicarbonate, make the sodium sulfate salt that forms after sodium hydroxide and the effect of sulfuric acid, under the effect of Wingdale and lime, obtain regeneration, and the benefit of design not only is effectively to realize sodium hydroxide recycling in technological process like this, technology is simple, easy to operate, there are not obstacle in economic environmental protection, industrial application yet, the more important thing is that employed Wingdale and lime raw material are easy to get, with low cost, and whole technology, flow process is short, and the Wingdale that raw material lime obtains after using also can further use, can reach the purpose that reduces cost to greatest extent, the gypsum that Wingdale obtains after using can be used as product and sells, and technological process does not have waste water and dregs and produces, and is environmentally friendly.
Technology of the present invention no longer is simple laboratory method, but can be applied to the concrete technical process in the industry.The flow scheme design that the present invention is such from enterprise and environmental angle, can reach and both save cost; reduce the consumption of resource; protect the dual purpose of environment again, thereby flow process of the present invention being most important for enterprise, also is the development trend that meets technology.
Embodiment
Below in conjunction with embodiment, the present invention is further described, following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Negative vanadium anionite-exchange resin sodium hydroxide solution desorb obtains sodium vanadate solution, and sodium vanadate solution adds sulfuric acid adjust pH to～1.5 precipitations and separates out red vanadium, filters the mixing solutions that obtains red vanadium filter cake and contains sodium sulfate and sodium pyrosulfate.After precipitation, extraordinarily go into lime carbonate by 1.2 of formation sodium bicarbonate chemical reaction stoichiometric number in the liquid earlier, 35 ℃ are stirred 2 hours transition, filtration obtains gypsum and sodium hydrogen carbonate solution, and then extraordinarily go into calcium hydroxide in solution by 1.5 of sodium bicarbonate causticization chemical reaction stoichiometric number, 97 ℃ were stirred causticization 2 hours, filtered and obtained lime carbonate and regeneration sodium hydroxide solution.Liquid continued to use transition after lime carbonate returned precipitation, and sodium hydroxide solution returns negative vanadium anionite-exchange resin desorption cycle and uses.
Embodiment 2
Copper anode mud is handled the tellurium material that contains that produces and is stirred the leaching of adding sodium hydroxide, filters and obtains sodium tellurite solution.Sodium tellurite solution adds the sulfuric acid neutralization precipitation and separates out TeO
2, filter and obtain TeO
2Filter cake and metabisulfite solution.In metabisulfite solution, stir adding lime carbonate earlier by 1.2 times that form sodium bicarbonate chemical reaction stoichiometric number, and while carbonic acid gas regulator solution pH value～6.0,50 ℃ were stirred 1.5 hours, make and become sodium sulfate transition in the solution sodium bicarbonate, filtration obtains gypsum and sodium hydrogen carbonate solution, and then press 1.7 times of sodium bicarbonate causticization chemical reaction stoichiometric number and in solution, stir and add calcium oxide, 70 ℃ of causticizations 3.5 hours are filtered and are obtained lime carbonate and regenerated sodium hydroxide solution.Lime carbonate returns and continues sodium sulfate transition to use, and returns after sodium hydroxide solution concentrates to contain the tellurium material and leach and recycle.
Embodiment 3
The sodium sulfate crystal that obtains in the alkaline process process for making alumina is dissolved in water, extraordinarily go into lime carbonate by 1.8 of formation sodium bicarbonate chemical reaction stoichiometric number, and add the sulphur acid for adjusting pH value simultaneously, 60 ℃ were stirred 1 hour, make sodium sulfate become sodium bicarbonate transition, filter and obtain gypsum and sodium hydrogen carbonate solution, and then press 1.6 times of stirring adding calcium oxide of sodium bicarbonate causticization chemical reaction stoichiometric number, 105 ℃ of causticizations 1 hour are filtered and are obtained lime carbonate and regenerated sodium hydroxide solution.Lime carbonate returns and continues sodium sulfate transition to use, and returns bauxite alkali after sodium hydroxide solution concentrates and soaks operation and recycle.
Claims (3)
1. a method for recycling sodium hydroxide is characterized in that, may further comprise the steps:
(1) earlier in metabisulfite solution, sodium bisulfate or sodium sulfate and sodium pyrosulfate mixing solutions, extraordinarily go into the calcium carbonate powders of particle diameter by forming sodium bicarbonate chemical reaction stoichiometric number 1.0-3.0 less than 380um, and feed carbonic acid gas or add the pH value 3.0-9.0 of sulfuric acid regulation solution, make sodium sulfate salt, hydrogen sulfate sodium salt or sodium sulfate salt and hydrogen sulfate sodium salt, become sodium bicarbonate transition, filter and obtain gypsum and sodium hydrogen carbonate solution;
(2) and then by sodium bicarbonate causticization chemical reaction stoichiometric number 1.0-3.5 extraordinarily go into calcium oxide or calcium hydroxide in sodium hydrogen carbonate solution, carry out causticizing reaction, filtration obtains lime carbonate and regeneration sodium hydroxide solution, lime carbonate returns in (1) step and continues to use, the sodium hydroxide solution that regeneration obtains directly returns required technological cycle and uses, or returns required technological cycle with the form of soda-lye or sodium hydrate solid after concentrating and use.
2. method according to claim 1 is characterized in that, the reaction in (1) step is under 0-60 ℃, stirs 0.5-4.5 hour.
3. method according to claim 1 is characterized in that, described (2) step causticizing reaction condition is that 0-110 ℃ was stirred 1-3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101909028A CN101898770B (en) | 2010-06-03 | 2010-06-03 | Method for recycling sodium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101909028A CN101898770B (en) | 2010-06-03 | 2010-06-03 | Method for recycling sodium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101898770A CN101898770A (en) | 2010-12-01 |
| CN101898770B true CN101898770B (en) | 2011-12-14 |
Family
ID=43224757
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|---|---|---|---|
| CN2010101909028A Expired - Fee Related CN101898770B (en) | 2010-06-03 | 2010-06-03 | Method for recycling sodium hydroxide |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10995014B1 (en) | 2020-07-10 | 2021-05-04 | Northvolt Ab | Process for producing crystallized metal sulfates |
| CN112551552A (en) * | 2020-09-24 | 2021-03-26 | 宣城市楷昂化工有限公司 | Method for preparing sodium hydroxide by using carbon dioxide |
| CN112758959A (en) * | 2021-03-12 | 2021-05-07 | 自贡鸿鹤制药有限责任公司 | Preparation method of sodium bicarbonate |
| CN115724612B (en) * | 2022-12-01 | 2024-05-31 | 广东理工学院 | Calcium silicate board activator and application thereof in preparation of calcium silicate board |
| CN115676857A (en) * | 2022-12-19 | 2023-02-03 | 唐山润达纳米高新钙业有限公司 | Method for jointly producing lithium battery raw material, calcium carbonate and calcium sulfate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB422689A (en) * | 1933-08-19 | 1935-01-16 | Ig Farbenindustrie Ag | Process for the joint production of a caustic soda lye, poor in sodium chloride, and of glauber salt |
| CN88103072A (en) * | 1988-05-28 | 1988-11-09 | 邹凤祥 | Produce the method for sodium hydroxide with sodium sulfate |
| CN1148028A (en) * | 1995-10-18 | 1997-04-23 | 孙世宁 | Process for prodn. of caustic soda using natural soda as raw material |
| US7247284B1 (en) * | 2004-02-24 | 2007-07-24 | Seck Karl A | Method and apparatus for regeneration of flue gas scrubber caustic solutions |
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2010
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Granted publication date: 20111214 Termination date: 20130603 |