CN103551029B - Modification method for semi-dry sintering flue gas desulfurization ash - Google Patents
Modification method for semi-dry sintering flue gas desulfurization ash Download PDFInfo
- Publication number
- CN103551029B CN103551029B CN201310499106.6A CN201310499106A CN103551029B CN 103551029 B CN103551029 B CN 103551029B CN 201310499106 A CN201310499106 A CN 201310499106A CN 103551029 B CN103551029 B CN 103551029B
- Authority
- CN
- China
- Prior art keywords
- desulphurization
- desulfurization ash
- flue gas
- gas desulfurization
- sintering flue
- 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.)
- Expired - Fee Related
Links
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a modification method for semi-dry sintering flue gas desulfurization ash. The modification method comprises steps of grinding and sieving the semi-dry sintering flue gas desulfurization ash, then steeping in deionized water for modification, and steeping in 5-20% oxalic acid for modification. The modification method not only can well modify the desulfurization ash, lower the content of Cl and S in desulfurization ash, and collect and reuse S and Cl in the desulfurization ash so as to alleviate the problem of deficiency of S and Cl to a certain degree; comprehensive utilization of the desulfurization ash in construction materials such as cement and concrete can be realized so as to lower the production cost of the construction materials, and the desulfurization ash can also be used in medical treatment. The modification method is simple, efficient, and low in cost, and has a broad prospect.
Description
Technical field
The invention belongs to resource environment protection field, particularly relate to a kind of method of modifying of semidry method sintering flue gas desulfurization ash.
Background technology
SO in sintering process
2discharge capacity account for the 60-70% of steel-producing system discharge capacity.In recent years, country is to sinter fume SO
2discharge put into effect stricter policy.Therefore, SO in sintering machine production process is controlled
2discharge, be iron and steel enterprise SO
2the emphasis of Environmental capacity, simultaneously for realization " 12 " steel industry SO
2emission reduction targets has great importance.As Key Environmental Protection task that is national and local government, iron and steel enterprise's auxiliary construction sintering flue gas desulfurization project is imperative.
Under the overall background of environmental protection and economy, many large-type sinterers are provided with sintered flue gas desulfurization device, and the main method of sintering flue gas desulfurization has wet method, semidry method, dry method etc.In recent years, newly-built sintering fume desulphurization method is mainly based on semi-dry desulphurization method.Thereupon occur that new obstruction semidry method sintering fume desulphurization method is popularized and the bottleneck developed, i.e. the process of sintering flue gas desulfurization ash and problem of complex utilization.For Baosteel, its Desulphurization carries out landfill and direct marketing, but due to process, store, cost of transportation is high, the problems such as market cheaper, the market space are little, it is actual in Desulphurization process is in lossing state.If simply stacked, not only take a large amount of soils, also can cause serious secondary pollution to environment.Therefore, be one of current urgent problem to the comprehensive utilizating research of desulfurizing byproduct.
The physical and chemical performance of semidry method sintering flue gas desulfurization ash have impact on the ability of its comprehensive utilization, and the main component of sintering flue gas desulfurization ash is CaSO
3, CaSO
4, Ca (OH)
2deng material.Just because of the CaSO wherein containing a large amount of instability
3, constrain the utilization of semidry method sintering flue gas desulfurization ash on cement, Desulphurization has to pass through certain pretreatment, makes CaSO
3be oxidized to CaSO
4manufacture of cement could be applied in large quantities.In addition, owing to containing a certain amount of Cl element in sintering flue gas desulfurization ash, if be directly used in concrete by Desulphurization, the corrosion of reinforcing bar is likely caused.Therefore, sintering flue gas desulfurization ash has very large potential economic benefit, carries out modification have very large meaning to Desulphurization.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method of modifying of semidry method sintering flue gas desulfurization ash.Method of modifying of the present invention, for the problem of semidry method sintering flue gas desulfurization ash comprehensive utilization difficulty, adopts deionized water and oxalic acid solution to carry out dipping modification to Desulphurization respectively, to reduce the content of itself S and Cl, realizes the collection respectively to S and Cl simultaneously.This method of modifying is simple, efficient, cost is low.
For achieving the above object, the present invention takes following measure:
The method of modifying of semidry method sintering flue gas desulfurization ash of the present invention, comprises the steps:
(1) by the grinding of semidry method sintering flue gas desulfurization ash, cross 100 mesh sieves, obtain Desulphurization I;
(2) the Desulphurization I of step (1) gained be impregnated in deionized water, be heated to 40 ~ 70 DEG C, insulation 2 ~ 4h; Filter, filtrate is chlorate solution, and filter residue is Desulphurization II;
(3) the Desulphurization II of step (2) gained be impregnated in oxalic acid solution, be heated to 60 ~ 80 DEG C, insulated and stirred 4 ~ 8h, wherein adopt alkali liquor absorption SO
2gas; Filter, get filter residue and adopt deionization washing 3 ~ 4 times, dry at 70 DEG C, to obtain final product.
In above-mentioned method of modifying, in described step (2), the quality of Desulphurization I is 1g ︰ 10 ~ 40ml with the ratio of the volume of deionized water.
In above-mentioned method of modifying, the mass fraction of described step (3) mesoxalic acid solution is 5 ~ 20%; The described quality of Desulphurization II and the ratio of the volume of oxalic acid solution are 1 ~ 3g ︰, 20 ~ 40ml.。
In above-mentioned method of modifying, described oxalic acid solution is formulated through following method: added by oxalic acid in deionized water, is heated to 60 ~ 80 DEG C, and insulation 10 ~ 15min, to obtain final product.
In above-mentioned method of modifying, the alkali lye in described step (3) is sodium hydroxide solution.
According to the result of material phase analysis, in Desulphurization, Cl mainly exists with the form of chlorate, comprises CaCl
2, KCl etc.First Desulphurization impregnated in deionized water by the present invention, and suitably heats, and chlorate is fully dissolved, and filtration can obtain chlorate solution.Then the Desulphurization modified through deionized water being impregnated in mass fraction is in the oxalic acid solution of 5 ~ 20%.Oxalic acid is prevalent in nature, and oxalic acid and calcium sulfate, calcium sulfite react oxalic calcium, and calcium oxalate can be analyzed to calcium carbonate or calcium oxide through calcination, the comprehensive utilization of modified Desulphurization of being more convenient for.Because calcium oxalate is more insoluble in water than calcium sulfate, calcium sulfite, adopt the method for ion-exchange, make the S in Desulphurization a part of with SO
2the form of gas is by alkali liquor absorption, and a part is with SO
4 2-form be present in oxalic acid solution.The key reaction occurred in modifying process is as follows:
Ca(OH)
2+H
2C
2O
4→CaC
2O
4+H
2O
CaSO
4→Ca
2++SO
4 2-
CaSO
3→Ca
2++SO
3 2-
SO
3 2-+H
+→HSO
3 -
HSO
3 -+H
+→SO
2+H
2O
Ca
2++C
2O
4 2-→CaC
2O
4
Beneficial effect of the present invention is: prior art mainly adopts the method for roasting oxidation modification, to reach CaSO in Desulphurization
3be oxidized to CaSO
4, this series methods can solve in Desulphurization due to CaSO
3unstable and restrict the problem of Desulphurization comprehensive utilization, and fail to solve the problem that in Desulphurization, Cl content is high.Method of modifying of the present invention adopts deionized water and oxalic acid solution double dry sintering flue gas desulfurization ash to carry out dipping modification respectively, can not only good modification Desulphurization, reduce the content of Cl and S, realize its comprehensive utilization in the construction material such as cement, concrete, reduce the production cost of construction material, the aspects such as medical treatment can also be used to, realize the Collection utilization to S and Cl in Desulphurization simultaneously, wherein the collection rate of Cl is up to 98.68%, the collection rate of S, up to 97.1%, can slow down the deficient problem of China S, Cl resource to a certain extent.Method of modifying of the present invention avoids environmental problem while bringing economic benefit and social benefit, has a extensive future.
Detailed description of the invention
Below in conjunction with detailed description of the invention, summary of the invention of the present invention is described in further detail.Should understand, embodiments of the invention only unrestricted the present invention for illustration of the present invention, when not departing from the technology of the present invention thought, according to ordinary skill knowledge and customary means, the various replacement made and change, all should comprise within the scope of the invention.
Embodiment 1
(1). adopt 100 mesh sieve, double dry sintering flue gas desulfurization ash to sieve, continue screening after remaining bulky grain grinding, until whole mistake 100 mesh sieve, obtain Desulphurization I;
(2) impregnated in deionized water by the Desulphurization I of step (1) gained, wherein the quality of Desulphurization I and the ratio of the volume of deionized water are 1g ︰ 20ml; Be heated to 40 DEG C, insulation 4h; Filter, filtrate is chlorate solution, and filter residue is Desulphurization II;
(3) take 35g oxalic acid and add 665ml deionized water, be heated to 60 DEG C, insulation 15min, obtains the oxalic acid solution that mass fraction is 5%;
(4) be impregnated in by the Desulphurization II of step (2) gained in the oxalic acid solution of step (3) gained, wherein the quality of Desulphurization II and the ratio of the volume of oxalic acid solution are 3g ︰ 20ml; Be heated to 50 DEG C, insulated and stirred 8h, wherein employing mass fraction is the sodium hydroxide solution absorption SO of 10%
2gas; Filter, get filter residue and adopt deionization to wash 3 times, dry at 70 DEG C, obtain Desulphurization A.
Double dry sintering flue gas desulfurization ash (former state Desulphurization), depart from grey II and Desulphurization A carries out constituent analysis respectively, result is as shown in the table:
The constituent analysis of table 1 Desulphurization
From data in table, Desulphurization floods modified through deionized water and oxalic acid solution first, significantly reduces the content of S and Cl in Desulphurization.In the present embodiment Desulphurization, the collection rate of Cl is the collection rate of 98.42%, S is 93.5%.
Embodiment 2
(1). adopt 100 mesh sieve, double dry sintering flue gas desulfurization ash to sieve, continue screening after remaining bulky grain grinding, until whole mistake 100 mesh sieve, obtain Desulphurization I;
(2) impregnated in deionized water by the Desulphurization I of step (1) gained, wherein the quality of Desulphurization I and the ratio of the volume of deionized water are 1g ︰ 10ml; Be heated to 60 DEG C, insulation 3h; Filter, filtrate is chlorate solution, and filter residue is Desulphurization II;
(3) take 70g oxalic acid and add 630ml deionized water, be heated to 70 DEG C, insulation 12min, obtains the oxalic acid solution that mass fraction is 10%;
(4) be impregnated in by the Desulphurization II of step (2) gained in the oxalic acid solution of step (3) gained, wherein the quality of Desulphurization II and the ratio of the volume of oxalic acid solution are 1g ︰ 20ml; Be heated to 60 DEG C, insulated and stirred 5h, wherein employing mass fraction is the sodium hydroxide solution absorption SO of 10%
2gas; Filter, get filter residue and adopt deionization to wash 4 times, dry at 70 DEG C, obtain Desulphurization B.
Double dry sintering flue gas desulfurization ash (former state Desulphurization), Desulphurization II and Desulphurization B carry out constituent analysis respectively, and result is as shown in the table:
The constituent analysis of table 2 Desulphurization
From data in table, Desulphurization floods modified through deionized water and oxalic acid solution first, significantly reduces the content of S and Cl in Desulphurization.In the present embodiment Desulphurization, the collection rate of Cl is the collection rate of 98.68%, S is 97.1%.
Embodiment 3
(1). adopt 100 mesh sieve, double dry sintering flue gas desulfurization ash to sieve, continue screening after remaining bulky grain grinding, until whole mistake 100 mesh sieve, obtain Desulphurization I;
(2) impregnated in deionized water by the Desulphurization I of step (1) gained, wherein the quality of Desulphurization I and the ratio of the volume of deionized water are 1g ︰ 40ml; Be heated to 70 DEG C, insulation 2h; Filter, filtrate is chlorate solution, and filter residue is Desulphurization II;
(3) take 140g oxalic acid and add 560ml deionized water, be heated to 80 DEG C, insulation 10min, obtains the oxalic acid solution that mass fraction is 20%;
(4) be impregnated in by the Desulphurization II of step (2) gained in the oxalic acid solution of step (3) gained, wherein the quality of Desulphurization II and the ratio of the volume of oxalic acid solution are 1g ︰ 40ml; Be heated to 50 DEG C, insulated and stirred 6h, wherein employing mass fraction is the sodium hydroxide solution absorption SO of 10%
2gas; Filter, get filter residue and adopt deionization to wash 4 times, dry at 70 DEG C, obtain Desulphurization C.
Double dry sintering flue gas desulfurization ash (former state Desulphurization), Desulphurization II and Desulphurization C carry out constituent analysis respectively, and result is as shown in the table:
From data in table, Desulphurization floods modified through deionized water and oxalic acid solution first, significantly reduces the content of S and Cl in Desulphurization.In the present embodiment Desulphurization, the collection rate of Cl is the collection rate of 98.54%, S is 90.2%.
The modified Desulphurization of the present invention is stripped of S, Cl, can reduce the corrosiveness that Cl causes coagulation reinforcing bar, and effectively remove CaSO3, Desulphurization can be avoided to decompose in calcination process when doing building materials and generate SO
2the secondary pollution caused, in modified Desulphurization, main component is calcium oxalate, and when doing building materials, calcining and decomposing can produce CO
2, CaCO
3, CaO etc., the secondary pollution of environment can not be brought, simultaneously CaCO
3the additive in production of construction materials is all can be used for CaO.Because in modified Desulphurization, main component is calcium oxalate, therefore through the Desulphurization that the inventive method is modified, the aspects such as medical treatment can also be used to.And collect S, Cl of obtaining in modifying process respectively and may be used for producing the commercial acid such as sulfuric acid, hydrochloric acid, a difficult problem for China S, Cl scarcity of resources can be alleviated to a certain extent.
Claims (3)
1. a method of modifying for semidry method sintering flue gas desulfurization ash, is characterized in that, comprises the steps:
(1) by the grinding of semidry method sintering flue gas desulfurization ash, cross 100 mesh sieves, obtain Desulphurization I;
(2) the Desulphurization I of step (1) gained be impregnated in deionized water, be heated to 40 ~ 70 DEG C, insulation 2 ~ 4h; Filter, filtrate is chlorate solution, and filter residue is Desulphurization II;
(3) the Desulphurization II of step (2) gained being impregnated in mass fraction is in the oxalic acid solution of 5 ~ 20%, is heated to 60 ~ 80 DEG C, insulated and stirred 4 ~ 8h, wherein adopts alkali liquor absorption SO
2gas; Filter, get filter residue and adopt deionization washing 3 ~ 4 times, dry at 70 DEG C, to obtain final product.
2. according to the method for modifying described in claim 1, it is characterized in that: in described step (2), the quality of Desulphurization I is 1g ︰ 10 ~ 40ml with the ratio of the volume of deionized water.
3. according to the method for modifying described in claim 1, it is characterized in that: the alkali lye in described step (3) is sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310499106.6A CN103551029B (en) | 2013-10-22 | 2013-10-22 | Modification method for semi-dry sintering flue gas desulfurization ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310499106.6A CN103551029B (en) | 2013-10-22 | 2013-10-22 | Modification method for semi-dry sintering flue gas desulfurization ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103551029A CN103551029A (en) | 2014-02-05 |
| CN103551029B true CN103551029B (en) | 2015-05-06 |
Family
ID=50005491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310499106.6A Expired - Fee Related CN103551029B (en) | 2013-10-22 | 2013-10-22 | Modification method for semi-dry sintering flue gas desulfurization ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103551029B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107399754A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of pro-oxygenic agent for being used to sinter the oxidation of flue gas semi-dry desulphurization ash |
| CN107399752A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of method for sintering flue gas semi-dry desulphurization ash acid oxidation modification |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104998885A (en) * | 2015-03-06 | 2015-10-28 | 大峘集团有限公司 | Water-saving desulfurized ash dechlorinating method and device |
| CN107400929B (en) * | 2017-03-03 | 2019-07-09 | 安徽工业大学 | A method of the sintering flue gas semi-dry desulphurization ash based on acid oxidation prepares calcium sulfate crystal whiskers |
| CN107399753B (en) * | 2017-03-03 | 2023-05-26 | 安徽工业大学 | Device and method for oxidative modification of sintering semi-dry desulfurization ash |
| CN109482049B (en) * | 2019-01-02 | 2021-07-23 | 武汉科林化工集团有限公司 | Dry desulfurization, denitrification and purification integrated process for coke oven flue gas |
| CN110421130A (en) * | 2019-06-04 | 2019-11-08 | 重庆大学 | The efficient separation method of sulphur in a kind of coal-fired flue-gas wet desulphurization gypsum |
| CN114105343B (en) * | 2020-08-26 | 2023-06-13 | 宝山钢铁股份有限公司 | Method for cooperatively treating desulfurization ash by desulfurization wastewater treatment system and application |
| CN112939050B (en) * | 2021-02-19 | 2023-08-22 | 北京铝能清新环境技术有限公司 | Resource utilization process suitable for semi-dry desulfurization waste ash in electrolytic aluminum industry |
| CN113603479A (en) * | 2021-09-18 | 2021-11-05 | 安徽马钢矿业资源集团南山矿业有限公司 | Preparation method of modified barium titanate foamed ceramic material and material obtained by preparation method |
| CN113651637A (en) * | 2021-09-18 | 2021-11-16 | 安徽马钢矿业资源集团南山矿业有限公司 | Preparation method of foamed ceramic thermal insulation material and material obtained by preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717218A (en) * | 2009-12-02 | 2010-06-02 | 江苏大峘集团有限公司 | Composite blend of semi-dry desulphurization ash and slag and preparation method thereof |
| CN102153301A (en) * | 2011-03-24 | 2011-08-17 | 广州市越堡水泥有限公司 | Method for preparing modified desulphurized ash |
| CA2821512A1 (en) * | 2010-12-17 | 2012-06-21 | The Catholic University Of America | Geopolymer composite for ultra high performance concrete |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007191670A (en) * | 2006-01-20 | 2007-08-02 | Institute Of Strategy For Sustainable Solutions Co Ltd | System for producing alkaline soil-improving material, combined with flue-gas desulfurization |
| US7863224B2 (en) * | 2009-03-17 | 2011-01-04 | Halliburton Energy Services Inc. | Wellbore servicing compositions comprising a set retarding agent and methods of making and using same |
-
2013
- 2013-10-22 CN CN201310499106.6A patent/CN103551029B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717218A (en) * | 2009-12-02 | 2010-06-02 | 江苏大峘集团有限公司 | Composite blend of semi-dry desulphurization ash and slag and preparation method thereof |
| CA2821512A1 (en) * | 2010-12-17 | 2012-06-21 | The Catholic University Of America | Geopolymer composite for ultra high performance concrete |
| CN102153301A (en) * | 2011-03-24 | 2011-08-17 | 广州市越堡水泥有限公司 | Method for preparing modified desulphurized ash |
Non-Patent Citations (1)
| Title |
|---|
| 半干法脱硫灰中CaSO3低温转化技术研究;李茜;《工程科技Ⅰ辑》;20111215;全文 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107399754A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of pro-oxygenic agent for being used to sinter the oxidation of flue gas semi-dry desulphurization ash |
| CN107399752A (en) * | 2017-03-03 | 2017-11-28 | 安徽工业大学 | A kind of method for sintering flue gas semi-dry desulphurization ash acid oxidation modification |
| CN107399754B (en) * | 2017-03-03 | 2019-01-22 | 安徽工业大学 | A kind of pro-oxygenic agent for the oxidation of sintering flue gas semi-dry desulphurization ash |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103551029A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103551029B (en) | Modification method for semi-dry sintering flue gas desulfurization ash | |
| CN103205570B (en) | Bone coal navajoite and pyrolusite together produce the method for Vanadium Pentoxide in FLAKES by-product manganese sulfate | |
| CN102703715B (en) | Method for recovering rhenium and molybdenum from rhenium and molybdenum-containing concentrate calcination flue dust | |
| CN105903333B (en) | A kind of flue gas process for deep desulphurization of magnesium fortified red mud | |
| CN107537492A (en) | A kind of method that iron system denitrating catalyst is directly prepared by the activation of red mud soda acid | |
| CN103706325A (en) | Preparation method of lithium slag adsorbent for liquid extraction of lithium | |
| CN103111264B (en) | The preparation method of a kind of ionic liquid and the two modification bacterium slag active carbon of metal and application | |
| CN103028313B (en) | Integrated desulfuration and denitration method for wet oxidation of flue gas | |
| CN103408052A (en) | Decomposition method of ardealite | |
| CN104084041B (en) | A kind of zinc oxide desulfurization gives up the renovation process of agent | |
| CN104004919A (en) | Environment-friendly recycling process of waste residues in electrolytic manganese production | |
| CN114702055A (en) | Method for preparing high-purity calcium carbonate from high-calcium fly ash by using recyclable amino acid leaching agent | |
| CN109988902B (en) | Method for dealkalizing iron-reinforced red mud and separating and recovering iron | |
| CN103936134B (en) | A kind of method utilizing synthetic ammonia gasification Slag treatment phenolic wastewater | |
| CN102070287B (en) | Process for reducing chloride ions in white mud from ammonia soda plants | |
| CN113769564A (en) | Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof | |
| CN105664708A (en) | CO2 absorbent as well as preparation method and application method thereof | |
| CN104162403B (en) | A kind of mixed acid modified calcium-based adsorbent and its preparation method and application | |
| CN102188896A (en) | Process for preparing complex desulfurizer from carbide slag for desulfuration | |
| CN103691283A (en) | Method for fixing carbon dioxide in industrial smoke | |
| CN111014230A (en) | Low-temperature oxidation method of dry-method and semi-dry-method desulfurized ash | |
| CN111410223A (en) | Method for recycling carbon resources in phosphate tailings | |
| CN102671523A (en) | Method for fixing light calcium carbonate as CO2 byproduct by using humate and desulfurization gypsum | |
| CN102888242B (en) | Method for decreasing FCC regenerative process NOx by DeNOx additive | |
| CN108296267A (en) | The method that industrial treatment is sintered red mud |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150506 Termination date: 20161022 |