CN1843966A - Method for treating waste acid liquor - Google Patents

Method for treating waste acid liquor Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
acid
calcium
manganese
waste liquid
iron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200610039980
Other languages
Chinese (zh)
Other versions
CN100361905C (en
Inventor
王水平
丁四宜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YUHE METAL MATERIAL CO Ltd CHANGZHOU CITY
Original Assignee
YUHE METAL MATERIAL CO Ltd CHANGZHOU CITY
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by YUHE METAL MATERIAL CO Ltd CHANGZHOU CITY filed Critical YUHE METAL MATERIAL CO Ltd CHANGZHOU CITY
Priority to CNB2006100399801A priority Critical patent/CN100361905C/en
Publication of CN1843966A publication Critical patent/CN1843966A/en
Application granted granted Critical
Publication of CN100361905C publication Critical patent/CN100361905C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Removal Of Specific Substances (AREA)

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

Treatment method of pickling waste liquid
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.
CNB2006100399801A 2006-04-28 2006-04-28 Method for treating waste acid liquor Expired - Fee Related CN100361905C (en)

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

Family

ID=37062936

Family Applications (1)

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

Country Status (1)

Country Link
CN (1) CN100361905C (en)

Cited By (12)

* Cited by examiner, † Cited by third party
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
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
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
CN116904994A (en) * 2023-07-18 2023-10-20 西北工业大学 A pickling solution and pickling method for GH4169 alloy pipes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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 Method for recovering iron oxide red and ammonium sulfate from pickling waste liquid
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 reclaiming and recovering acid mixed liquid such as waste liquid of hydrofluoric acid

Cited By (16)

* Cited by examiner, † Cited by third party
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 A method for recycling waste liquid used in photovoltaic black silicon wafer production line
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
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
CN113120938B (en) * 2020-01-16 2022-09-20 中国科学院过程工程研究所 A kind of method utilizing fluorine-containing wastewater to prepare calcium fluoride
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
CN116904994A (en) * 2023-07-18 2023-10-20 西北工业大学 A pickling solution and pickling method for GH4169 alloy pipes

Also Published As

Publication number Publication date
CN100361905C (en) 2008-01-16

Similar Documents

Publication Publication Date Title
CN1843966A (en) Method for treating waste acid liquor
CN101353210B (en) Method for processing aluminum section bar chromizing waste water with calcium sulfite type desulphurization mortar
CN106277006B (en) A kind of method for refined crystalline aluminium chloride deliming
CN1803660A (en) High-efficiency environment-friendly acid-mixed plating removal liquor
CN103588240A (en) Green utilization method of waste acid
WO2024212479A1 (en) Method for leaching scheelite
CN100337906C (en) High-pollution low-concentration waste acid recycling method
CN1281820A (en) Technological process for producing aluminium salt and silicate by using coal gangue
CN1035109C (en) Method for producing cuprous chloride by using waste copper chloride etching solution
CN110257624B (en) Arsenic removing method for arsenic-containing smoke dust
JP2009233605A (en) Treatment method of boron fluoride-containing water
CN1111205C (en) Method of treating arsenic alkaline slag from antimony smelting
CN105543500B (en) The method that reclaims zinc is discarded in mud cake containing zinc from electrogalvanizing
CN1010956B (en) Regeneration Method of Titanium and Titanium Alloy Pickling Waste Liquid
CN1899971A (en) Method for extracting V2O5 from stone coal vanadium ore
CN102060335B (en) Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry
CN107513682B (en) A kind of zincincation of acid circulation
CN1041404C (en) Method for removing bromate from lithium bromide solution
CN1258642A (en) Continuous precipitation process of prodcing globular ammonium polyvanadate
CN105481001B (en) Optimized method for recycling electrogalvanizing waste zinc
CN111517534B (en) Waste acid recycling process
CN103803737A (en) Treatment method of copper-containing etching liquid
CN115105857A (en) Purifying treatment agent and purifying method for tributyl phosphate waste organic phase
CN1142543A (en) Treating method for waste alkali etching liquid of printed circuit boards
CN1138704C (en) Method for treatment of waste lye

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080116

Termination date: 20120428