CN1843966A - Method for treating waste acid liquor - Google Patents
Method for treating waste acid liquor Download PDFInfo
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- CN1843966A CN1843966A CN 200610039980 CN200610039980A CN1843966A CN 1843966 A CN1843966 A CN 1843966A CN 200610039980 CN200610039980 CN 200610039980 CN 200610039980 A CN200610039980 A CN 200610039980A CN 1843966 A CN1843966 A CN 1843966A
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Abstract
The invention relates to a handling method of acid washing liquor, in particular to a handling method of acid washing liquor containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ion, iron ion and so on. The method comprises the following steps: firstly, adding said acid washing liquor into retort, adding sodium carbonate or natrium hydroxydatum for neutralization until PH value reaches to 3-3.5; secondly, adding calcium carbonate to react with hydrofluoric acid to get calcium fluoride precipitation, react with fluosilicic acid to get calcium silicofluoride precipitation; thirdly, adding sodium carbonate until PH value reaches to 7.5-8, to react with manganese ion, iron ion to get their oxides precipitation; fourthly, filtering, filter residue are oxides of manganese and iron, calcium fluoride and calcium silicofluoride, and concentrating and crystallizing filter liquor to get the product of sodium nitrate. The invention makes full use of valuable ingredient, with no secondary pollution, secondary pollution, low cost and high-purity material finished product.
Description
Technical Field
The invention relates to a treatment method of pickling waste liquid, in particular to a treatment method of pickling waste liquid containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ions, iron ions and the like.
Background
The pickling waste liquid is an industrial treatment waste liquid, the components of the pickling waste liquid are different, the pickling waste liquid mainly contains about 60 percent of nitric acid, about 10 percent of hydrofluoric acid and a small amount of fluosilicic acid, manganese ions, iron ions and the like, if the pickling waste liquid is directly discharged, the environmental pollution and the waste of valuable components can be caused, and the requirement of environmental protection can not be met, so the pickling waste liquid needs to be treated, a neutralization method is generally adopted for treating the waste liquid at present, the pickling waste liquid is neutralized to be neutral, and then the neutralization method is diluted and discharged, and the treatment method has the following defects: (1) valuable components in the pickling waste liquid cannot be fully utilized, so that a large amount of energy is wasted; (2) many harmful components are discharged as waste water and waste after treatment, so that secondary pollution is caused; (3) and the treatment cost of the pickling waste liquid is high. However, a method which can effectively and radically cure secondary pollution and effectively utilize valuable components in the pickling waste liquid cannot be found at present, which is a problem that cannot be solved all the time.
Disclosure of Invention
The invention aims to provide a method for treating the pickling waste liquid, which can save resources, reduce cost, protect environment and fully utilize valuable components, aiming at the defects of the prior art.
The technical scheme for realizing the purpose is as follows: a method for treating pickling waste liquid comprises the following steps:
firstly, putting pickling waste liquid containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ions, iron ions and the like into a reaction tank, and adding sodium carbonate or sodium hydroxide for neutralization until the pH value reaches 3-3.5;
secondly, adding calcium carbonate to separate out hydrofluoric acid in the form of calcium fluoride precipitate, and separating out fluosilicic acid in the form of calcium fluosilicate precipitate;
thirdly, adding sodium carbonate until the pH value reaches 7.5-8, and separating out manganese ions and iron ions in the form of oxides;
and fourthly, filtering, wherein filter residues are manganese oxide, iron oxide, calcium fluoride and calcium fluosilicate products, and concentrating and crystallizing the filtrate sodium nitrate to obtain a sodium nitrate product.
The main chemical reaction formula of the invention is as follows:
(1)
(2)
(3)
(4)
(5)
(6)
the invention adopting the method for treating the pickling waste liquid has the advantages that: (1) the treatment method can treat valuable components of nitric acid, hydrofluoric acid, fluosilicic acid and manganese and iron ions in the pickling waste liquid, and manganese, iron oxide, sodium nitrate, calcium fluoride and calcium fluosilicate products can be obtained after treatment. The sodium nitrate product can be used as raw material for preparing potassium nitrate, explosive, picric acid dye, etc., also can be used as glass defoaming agent, fluxing agent and oxidant for enamel industry, tobacco combustion improver, metal cleaning agent, culture agent for penicillin, aluminium alloy heat treatment agent and decolouring agent for molten caustic soda, etc., also can be used as fertilizer in agriculture, and is a product which is very popular and beautiful in the market, manganese, iron oxide, calcium fluoride and calcium fluosilicate products, and has stable chemical property, no pollution and water insolubility, and can be used as building filler, so that the building cost is greatly reduced. The treatment method changes waste into valuable, realizes the reutilization of resources, and increases the economic added value; (2) the treatment method has no pollutant discharge, reduces the use cost and the treatment cost, avoids secondary pollution, realizes the thorough radical treatment of the pickling waste liquid, and is a novel, environment-friendly, cost-reducing and efficiency-improving treatment method. (3) The final product obtained by the treatment method has high purity.
Drawings
FIG. 1 is a block diagram of a process flow of the present invention.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples.
Example one
As shown in fig. 1, a method for treating a spent pickling solution comprises the following steps: firstly, putting pickling waste liquid containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ions, iron ions and the like into a reaction tank, and adding sodium carbonate or sodium hydroxide for neutralization until the PH reaches 3; then adding calcium carbonate to separate out hydrofluoric acid in the form of calcium fluoride precipitate, and separating out fluosilicic acid in the form of calcium fluosilicate precipitate; then adding sodium carbonate until the PH value reaches 8, so that manganese ions and iron ions are separated out in the form of oxides thereof; then heating to more than 80 ℃, stirring and preserving heat for 30 minutes; and finally, filtering, wherein filter residues are manganese oxide, iron oxide, calcium fluoride and calcium fluosilicate products, and concentrating and crystallizing filtrate sodium nitrate to obtain a sodium nitrate product.
Example two
As shown in fig. 1, a method for treating a spent pickling solution comprises the following steps: firstly, putting pickling waste liquid containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ions, iron ions and the like into a reaction tank, and adding sodium carbonate or sodium hydroxide for neutralization until the pH value reaches 3.5; then adding calcium carbonate to separate out hydrofluoric acid in the form of calcium fluoride precipitate, and separating out fluosilicic acid in the form of calcium fluosilicate precipitate; then adding sodium carbonate until the PH value reaches 7.5, so that manganese ions and iron ions are separated out in the form of oxides thereof; then heating to more than 80 ℃, stirring and preserving heat for 30 minutes; and finally, filtering, wherein filter residues are manganese oxide, iron oxide, calcium fluoride and calcium fluosilicate products, and concentrating and crystallizing filtrate sodium nitrate to obtain a sodium nitrate product.
In addition to adding sodium carbonate to separate out manganese and iron ions in the form of their oxides, the present invention can also separate out manganese and iron ions in the form of their oxides by adding sodium carbonate and sodium hydroxide.
In the process of treating the pickling waste liquid, the generated nitrogen oxide gas can be completely absorbed by liquid alkali, and the generated sodium nitrate and sodium nitrite can enter a sodium nitrate route, so that the method is very environment-friendly on one hand, and waste is avoided on the other hand.
Claims (3)
1. A treatment method of pickling waste liquid is characterized by comprising the following steps: the method comprises the following steps:
firstly, putting pickling waste liquid containing nitric acid, hydrofluoric acid, fluosilicic acid, manganese ions, iron ions and the like into a reaction tank, and adding sodium carbonate or sodium hydroxide for neutralization until the pH value reaches 3-3.5;
secondly, adding calcium carbonate to separate out hydrofluoric acid in the form of calcium fluoride precipitate, and separating out fluosilicic acid in the form of calcium fluosilicate precipitate;
thirdly, adding sodium carbonate until the pH value reaches 7.5-8, and separating out manganese ions and iron ions in the form of oxides;
and fourthly, filtering, wherein filter residues are manganese oxide, iron oxide, calcium fluoride and calcium fluosilicate products, and concentrating and crystallizing the filtrate sodium nitrate to obtain a sodium nitrate product.
2. The method for treating a spent pickling solution according to claim 1, characterized in that: the pH in the first step reached 3 and the pH in the third step reached 8.
3. The method for treating a spent pickling solution according to claim 1, characterized in that: the pH in the first step reached 3.5 and the pH in the third step reached 7.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100399801A CN100361905C (en) | 2006-04-28 | 2006-04-28 | Method for treating waste acid liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100399801A CN100361905C (en) | 2006-04-28 | 2006-04-28 | Method for treating waste acid liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1843966A true CN1843966A (en) | 2006-10-11 |
| CN100361905C CN100361905C (en) | 2008-01-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100399801A Expired - Fee Related CN100361905C (en) | 2006-04-28 | 2006-04-28 | Method for treating waste acid liquor |
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| CN (1) | CN100361905C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092719A (en) * | 2011-01-14 | 2011-06-15 | 云南常青树化工有限公司 | Method for producing industrial calcium fluosilicate |
| CN102417881A (en) * | 2010-09-27 | 2012-04-18 | 新奥科技发展有限公司 | Application of waste acid in microalgae industry |
| CN104071927A (en) * | 2014-07-14 | 2014-10-01 | 湖南水口山有色金属集团有限公司 | Acid-making sewage treatment system and method |
| CN104973580A (en) * | 2015-07-02 | 2015-10-14 | 苏州晶洲装备科技有限公司 | Collecting and recycling method of polycrystalline silicon texturing etching waste liquid |
| CN105036404A (en) * | 2015-06-30 | 2015-11-11 | 田辉明 | Zero discharge treatment method for acid wastewater generated by acid pickling and purification of quartz sand powder or feldspar sand powder |
| CN105385851A (en) * | 2015-11-04 | 2016-03-09 | 浙江盛达铁塔有限公司 | Treatment method of acid pickling waste liquid |
| CN108046270A (en) * | 2017-12-14 | 2018-05-18 | 江西渠成氟化学有限公司 | A kind of recovery and treatment method of nitration mixture |
| CN108642298A (en) * | 2018-04-24 | 2018-10-12 | 山东建筑大学 | A kind of black silicon wafer production line method for recovering waste liquid of photovoltaic |
| CN112520776A (en) * | 2020-11-26 | 2021-03-19 | 广沣金源（北京）科技有限公司 | Combined treatment method for fluorine-containing nitric acid waste liquid and hydrofluoric acid waste liquid |
| CN113120937A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院过程工程研究所 | Comprehensive utilization method of fluorine-containing silicic acid wastewater |
| CN113120938A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院过程工程研究所 | Method for preparing calcium fluoride by using fluorine-containing wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1010956B (en) * | 1986-06-24 | 1990-12-26 | 宝鸡稀有金属加工研究所 | Regeneration Method of Titanium and Titanium Alloy Pickling Waste Liquid |
| CN1009547B (en) * | 1987-05-06 | 1990-09-12 | 黄卓林 | Recovery technique of iron oxide red and ammonia sulphate from waste liquid of pickle |
| JPH0489315A (en) * | 1990-07-30 | 1992-03-23 | Toagosei Chem Ind Co Ltd | Method for recovering copper sulfate and alkali chloride from aqueous copper chloride solution containing hydrochoric acid |
| JPH09176874A (en) * | 1995-12-21 | 1997-07-08 | Shinko Pantec Co Ltd | Method for regenerating and recovering acid liquid mixture such as waste nitric acid-hydrofluoric acid mixture |
-
2006
- 2006-04-28 CN CNB2006100399801A patent/CN100361905C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417881A (en) * | 2010-09-27 | 2012-04-18 | 新奥科技发展有限公司 | Application of waste acid in microalgae industry |
| CN102417881B (en) * | 2010-09-27 | 2015-04-29 | 新奥科技发展有限公司 | Application of waste acid in microalgae industry |
| CN102092719A (en) * | 2011-01-14 | 2011-06-15 | 云南常青树化工有限公司 | Method for producing industrial calcium fluosilicate |
| CN102092719B (en) * | 2011-01-14 | 2013-01-23 | 云南常青树化工有限公司 | Method for producing industrial calcium fluosilicate |
| CN104071927A (en) * | 2014-07-14 | 2014-10-01 | 湖南水口山有色金属集团有限公司 | Acid-making sewage treatment system and method |
| CN105036404A (en) * | 2015-06-30 | 2015-11-11 | 田辉明 | Zero discharge treatment method for acid wastewater generated by acid pickling and purification of quartz sand powder or feldspar sand powder |
| CN104973580A (en) * | 2015-07-02 | 2015-10-14 | 苏州晶洲装备科技有限公司 | Collecting and recycling method of polycrystalline silicon texturing etching waste liquid |
| CN105385851A (en) * | 2015-11-04 | 2016-03-09 | 浙江盛达铁塔有限公司 | Treatment method of acid pickling waste liquid |
| CN108046270A (en) * | 2017-12-14 | 2018-05-18 | 江西渠成氟化学有限公司 | A kind of recovery and treatment method of nitration mixture |
| CN108642298A (en) * | 2018-04-24 | 2018-10-12 | 山东建筑大学 | A kind of black silicon wafer production line method for recovering waste liquid of photovoltaic |
| CN108642298B (en) * | 2018-04-24 | 2020-05-26 | 山东建筑大学 | Waste liquid recovery method for photovoltaic black silicon wafer production line |
| CN113120937A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院过程工程研究所 | Comprehensive utilization method of fluorine-containing silicic acid wastewater |
| CN113120938A (en) * | 2020-01-16 | 2021-07-16 | 中国科学院过程工程研究所 | Method for preparing calcium fluoride by using fluorine-containing wastewater |
| CN113120938B (en) * | 2020-01-16 | 2022-09-20 | 中国科学院过程工程研究所 | Method for preparing calcium fluoride by using fluorine-containing wastewater |
| CN112520776A (en) * | 2020-11-26 | 2021-03-19 | 广沣金源（北京）科技有限公司 | Combined treatment method for fluorine-containing nitric acid waste liquid and hydrofluoric acid waste liquid |
Also Published As
| Publication number | Publication date |
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| CN100361905C (en) | 2008-01-16 |
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