CN1063730C - Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid - Google Patents
Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid Download PDFInfo
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- CN1063730C CN1063730C CN98111575A CN98111575A CN1063730C CN 1063730 C CN1063730 C CN 1063730C CN 98111575 A CN98111575 A CN 98111575A CN 98111575 A CN98111575 A CN 98111575A CN 1063730 C CN1063730 C CN 1063730C
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- magnesium sulfate
- sulfuric acid
- waste sulfuric
- titanium dioxide
- acid solution
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Abstract
The present invention relates to a technology for producing magnesium sulfate in the treatment of waste sulfuric acid liquid of titanium dioxide. Waste sulfuric acid liquid of titanium dioxide is mixed with magnesite or magnesium oxide, and the mixture is stirred so as to sufficiently carry out an ion exchange reaction; after the sufficient reaction, clear liquid of magnesium sulfate is obtained through pressure filtration and separation; solid magnesium sulfate is obtained through vaporizing concentration, cooling crystallization and centrifugal filtration. Through the present invention, impurities are successfully separated from the waste sulfuric acid liquid of titanium dioxide, effective ingredients are fully utilized, and no waste liquid is discharged. The technology has the advantage of simplicity, the problems existing in environmental protection are solved, output magnesium sulfate obtains good economic benefit, and filtration residue is comprehensively utilized for producing multi-element composite fertilizers of sulfur and magnesium.
Description
The invention relates to a waste liquid treatment process. In particular to a process for treating waste sulfuric acid discharged in the production process of titanium dioxide by an ion exchange method.
In the prior art, the production of titanium dioxide by a sulfuric acid method produces a large amount of waste sulfuric acid solution, the sulfuric acid concentration of which is as high as 35 percent and as low as 5 percent, and the waste sulfuric acid solution contains various impurities such as iron, manganese, titanium, vanadium and the like. Due to large discharge amount, high impurity content and various types, the impurity separation is difficult, so that the development and utilization of the impurities are difficult. For years, most enterprises directly discharge the red gypsum into rivers, lakes and seas or discharge the red gypsum after lime neutralization treatment, but the obtained red gypsum has no utilization value. The prior art adopting lime neutralization treatment has the following defects: the effective components in the waste liquid are not fully utilized, and the discharged waste liquid after treatment still pollutes the environment. For a long time, the problem of environmental protection caused by the discharge of waste sulfuric acid solution in the titanium dioxide production industry becomes a great problem.
The invention aims to provide a process for producing magnesium sulfate by adding magnesia or magnesia into the treatment of titanium dioxide waste sulfuric acid solution for ion exchange aiming at the defects of the prior art.
The invention aims to achieve the following technical scheme, and the invention relates to a process for producing magnesium sulfate in treatment of titanium dioxide waste sulfuric acid solution, which is characterized in that 10-38 parts of titanium dioxide waste sulfuric acid solution with the sulfuric acid reaction concentration of 10-22.5 percent and 2.8-6.0 parts of magnesiaor magnesia with the magnesium oxide content of 75-95 percent are mixed and stirred according to the weight ratio, so that the mixture is fully subjected to ion exchange reaction, filter pressing is carried out to separate out filter residue, magnesium sulfate filtrate is obtained, and the filtrate is evaporated, concentrated, cooled, crystallized and centrifugally filtered to obtain solid magnesium sulfate. The chemical reaction is that magnesia in magnesite reacts with waste sulfuric acid to produce magnesium sulfate, and the magnesite is hydrolyzed to produce precipitate of Fe, Mn, Cr and other elements and separate out.
The object of the present invention can be further achieved by the following means. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution is characterized in that before magnesia containing 75-95% of magnesium oxide or magnesium oxide is mixed with titanium dioxide waste sulfuric acid solution, under the condition of keeping reaction concentration unchanged, water is firstly added or mother liquor is circulated and stirred into uniform slurry, and then the uniform slurry and the titanium dioxide waste sulfuric acid solution are subjected to ion exchange reaction. The reactants are reacted uniformly, and the reaction speed is improved.
The object of the present invention can be further achieved by the following means. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid liquid is characterized in that 1.0-1.44 parts of magnesia or magnesium oxide containing 75-95% of magnesium oxide is added into magnesium sulfate filtrate separated by filter pressing according to weight per hundred parts of magnesium sulfate filtrate, hydrogen peroxide for enabling ferrous iron to become ferric iron is added for full reaction, filter pressing is carried out to separate filter residue, magnesium sulfate clear liquid is obtained, and evaporation concentration, cooling crystallization and centrifugal filtration are carried out to obtain crystallized magnesium sulfate. The reason is that when the amount of the magnesite is slightly deficient, fine adjustment supplement is carried out, and the hydrogen peroxide enables ferrous iron to become ferric iron, so that the removal rate of the iron is improved; thereby ensuring that the quality of the obtained crystal magnesium sulfate meets the requirement of industrial grade magnesium sulfate.
Fe2++H2O2→Fe3++H2O
The object of the present invention can be further achieved by the following means. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid liquid is characterized in that pure sulfuric acid is firstly used for titration in magnesium sulfate filtrate or clear liquid obtained by filter-pressing separation, the pH value is adjusted to 6-7, and then evaporation concentration, cooling crystallization and centrifugal filtration are carried out to obtain crystallized magnesium sulfate. Titration was performed to neutralize a slight excess of internal hydroxide.
The object of the present invention can be further achieved by the following means. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid liquid is characterized in that the separated filter residue is washed by water, and the washing liquid obtained by pressure filtration is added into the magnesium sulfate filtrate or recycled and added into the ion exchange reaction process for recycling.
The object of the present invention can be further achieved by the following means. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid liquid is characterized in that filter residue which contains magnesium, sulfur, iron and other elements and does not contain chlorine root and is obtained by filter pressing is dried into powder or is mixed with other types of fertilizers to prepare the multi-element sulfur-magnesium compound fertilizer.
Compared with the prior art, the invention adopts an ion exchange method to add magnesia or magnesia into the treatment of the waste sulfuric acid liquid of titanium dioxide to produce magnesium sulfate. Impurities in the titanium dioxide waste sulfuric acid solution are successfully separated, so that the effective components in the waste solution are fully utilized, no waste solution is discharged after treatment, and the separated filter residue is used for manufacturing the agricultural fertilizer. The invention has simple process and low investment, not only solves the environmental protection problem caused by the discharge of waste sulfuric acid liquid in the titanium dioxide production industry for a long time, but also can produce the magnesium sulfate product with larger economic benefit and good social benefit. The filter residue is used for producing the multi-element sulfur-magnesium compound fertilizer, so that the comprehensive utilization of the raw materials is realized.
FIG. 1 is a simplified process flow diagram of the present invention.
FIG. 2 is a process flow diagram of the cycle of the present invention.
The first embodiment. The following examples further illustrate the invention. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution of this embodiment is such that, as shown in the flow chart of fig. 1, 0.1 kg of magnesia (6 parts) with a magnesium oxide content of 75% is slowly added into a tank containing 2.0 kg (20 parts) of titanium dioxide waste sulfuric acid solution with a concentration of 28% according to each part, the reaction concentration of the magnesia is 22.3%, the mixture is stirred for 60 minutes to continue to react, after full action, filter residue is obtained by pressure filtration of 1.6 kg, magnesium sulfate filtrate of 1.0 kg is evaporated, concentrated and dehydrated by 0.45 kg, cooled and crystallized, and filtered by centrifugation to obtain MgSO4·7H288% of O and Fe2+0.4 kg of solid magnesium sulfate product with a content of 0.02% and 0.15 kg of mother liquor.
Example two. The following examples continue to describe the content of the present invention, and the process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution in this example is as follows: 0.28 kg (2.8 parts) of magnesium oxide with a content of 95% and 1.52 kg of water per 0.1 kg,after uniform size mixing, slowly adding the mixture into a container in which waste titanium dioxide sulfuric acid with the concentration of 28% is stored, wherein the reaction concentration of the sulfuric acid is 10%, stirring and reacting for 1 hour, allowing the mixture to continue to react, after full action, performing pressure filtration to obtain 0.875 kg of filter residue and 1.925 kg of magnesium sulfate filtrate, washing the filter residue with 0.5 kg of water, and performing pressure filtration to obtain 0.78 kg of filter residue and 0.595 kg of magnesium sulfate filtrate. Mixing the two magnesium sulfate filtrates to 2.52 kg, evaporating, concentrating, dehydrating to 1.755 kg, cooling, crystallizing, centrifuging, and filtering to obtain MgSO4·7H294% of O and Fe2+0.645 kg of solid magnesium sulfate product with a content of 0.05% and 0.12 kg of mother liquor. And mixing the two filter residues and adding a fertilizer.
Example three. The following examples continue to illustrate the inventive content of the present invention. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution in the embodiment is as follows: 0.48 kg (4.8 parts) of magnesia with the content of 85% and 1.55 kg (15.5 parts) of dilute waste sulfuric acid with the concentration of 5% are slowly added into a container which contains 2.25 kg (22.5 parts) of waste titanium dioxide sulfuric acid solution with the concentration of 35% according to 0.1 kg per part, the reaction concentration of the sulfuric acid is 20.21%, stirring is kept for 40 minutes, the reaction is continued, and after full action, the reaction product is subjected to pressure filtration to obtain 1.615 kg of filter residue and 2.665 kg of filtrate. The filter residue is mixed with 0.615 kg of water for pulp mixing and washing, and then the filter residue is pressed and filtered to obtain 1.15 kg of filter residue and 1.08 kg of filtrate. Mixing the two filtrates to 3.745 kg of magnesium sulfate filtrate, placing into another reactor, adding 0.054 kg of magnesite into the reactor, stirring for reacting sufficiently, press-filtering to obtain 0.08 kg of filter residue and 3.719 kg of clear magnesium sulfate filtrate, evaporating, concentrating, dehydrating 2.139 kg, cooling, crystallizing, centrifuging, and filtering to obtain MgSO4·7H2O content of 97.8%, Fe2+1.28 kg of crystalline magnesium sulfate product with a content of less than 0.03% and 0.3 kg of mother liquor. And mixing the two filter residues and adding a fertilizer.
Example four. The following examples continue to illustrate the inventive content of the present invention. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution in the embodiment is as follows: as shown in the flow chart of fig. 2, 0.35 kg per 0.1 kg serving was added(3.5 parts) magnesia with the magnesium oxide content of 85%, 0.98 kg of returned mother liquor and 0.18 kg of water are added into a size mixing tank, stirred for 0.5 hour and then fed into a reactor containing 2.0 kg (20 parts) of titanium dioxide waste sulfuric acid with the concentration of 28%, the reaction concentration of the sulfuric acid is 15.95%, the material is discharged after 1 hour of reaction, and after the material is fed into a storage tank for full reaction, 1.49 kg of filter residue and 2.02 kg of magnesium sulfate filtrate are obtained through pressure filtration; washing the filter residue in a size mixing barrel for 0.5 hour by using 0.6 kg of water, and then carrying out filter pressing to obtain 1.11 kg of filter residue and 0.98 kg of filtrate, wherein the filtrate is used as the returned mother liquor for recycling. Adding 0.02 kg of magnesia and 0.24 kg of centrifugal mother liquor returned by the rear process into 2.02 kg of magnesium sulfate filtrate obtained by filter pressing, adding 0.0055 kg of hydrogen peroxide, stirring and reacting for about 2 hours, then carrying out filter pressing to obtain 0.051 kg of filter residue, clarifying 2.2345 kg of magnesium sulfate filtrate, titrating to a pH value of 6-7 by using pure sulfuric acid, evaporating and concentrating to obtain 1.22 kg of finished solution after losing 1.0145 kg of water, cooling to 35 ℃ for crystallization, centrifuging and filtering by a centrifuge to obtain MgSO (magnesium sulfate)4·7H2O content is more than or equal to 98 percent, Fe2+0.98 kg of crystallized industrial magnesium sulfate heptahydrate product with the content less than or equal to 0.001 percent and 0.24 kg of centrifugal mother liquor, and the centrifugal mother liquor is recycled. The quality of the product meets the requirements of national industry standard HG/T2680-95 first-grade products. And drying the filter residue which is obtained by twice filter pressing and mainly contains elements such as magnesium, sulfur, iron and the like and does not contain chlorine radicals into powder, and mixing the powder with other types of fertilizers to obtain the multi-element sulfur-magnesium compound fertilizer.
Claims (6)
1. A process for producing magnesium sulfate in the treatment of titanium white waste sulfuric acid solution is characterized in that 10-38 parts of titanium white waste sulfuric acid solution with sulfuric acid reaction concentration adjusted to 10-22.5% and 2.8-6.0 parts of magnesia or magnesia with magnesium oxide content of 75-95% are mixed and stirred according to weight ratio to fully carry out ion exchange reaction, filter pressing is carried out to separate out filter residue to obtain magnesium sulfate filtrate, and the filtrate is evaporated, concentrated, cooled, crystallized and centrifugally filtered to obtain solid magnesium sulfate.
2. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution according to claim 1, which is characterized in that before magnesia containing 75-95% of magnesium oxide or magnesium oxide is mixed with titanium dioxide waste sulfuric acid solution, water or circulating mother liquor is added to stir into uniform slurry before the reaction concentration is kept unchanged, and then the uniform slurry and the titanium dioxide waste sulfuric acid solution are subjected to ion exchange reaction.
3. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution according to claim 1, which is characterized in that 1-1.4 parts by weight of magnesia or magnesium oxide containing 75-95% of magnesium oxide is added to the magnesium sulfate filtrate separated by pressure filtration, hydrogen peroxide for making ferrous iron become ferric iron is added for full reaction, then the filter residue is separated by pressure filtration, magnesium sulfate clear solution is obtained, and the crystal magnesium sulfate is obtained by evaporation concentration, cooling crystallization and centrifugal filtration.
4. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution according to claim 1 or 3, characterized in that pure sulfuric acid is firstly used for titration in magnesium sulfate filtrate or clear solution obtained by filter-pressing separation to adjust the pH value to 6-7, and then the crystallized magnesium sulfate is obtained by evaporation concentration, cooling crystallization and centrifugal filtration.
5. The process for producing magnesium sulfate in the treatment of titanium dioxide waste sulfuric acid solution according to claim 1 or 3, characterized in that the separated filter residue is washed with water, and the washing solution obtained by pressure filtration is added into the clear magnesium sulfate solution or recycled and added into the ion exchange reaction process for recycling.
6. The process for producing magnesium sulfate in treatment of titanium dioxide waste sulfuric acid solution according to claim 1 or 3, characterizedin that magnesium, sulfur and iron are contained in the titanium dioxide waste sulfuric acid solution obtained by pressure filtration
Drying the filter residue containing no chlorine radicals into powder or mixing with other fertilizers to prepare the multi-element sulfur-magnesium compound fertilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111575A CN1063730C (en) | 1998-11-13 | 1998-11-13 | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN98111575A CN1063730C (en) | 1998-11-13 | 1998-11-13 | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid |
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| CN1220970A CN1220970A (en) | 1999-06-30 |
| CN1063730C true CN1063730C (en) | 2001-03-28 |
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| CN98111575A Expired - Fee Related CN1063730C (en) | 1998-11-13 | 1998-11-13 | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331817C (en) * | 2003-08-02 | 2007-08-15 | 唐春森 | Method for producing agricultural granular magnesium sulfate fertilizer |
| US7473409B2 (en) * | 2006-08-30 | 2009-01-06 | Veolia Es Technical Solutions L.L.C. | Process for recycling waste acid |
| CN101555055B (en) * | 2009-05-20 | 2012-05-23 | 张小娟 | Compound decoloring and deodorizing coagulant and preparation process thereof |
| GB201115836D0 (en) | 2011-09-13 | 2011-10-26 | Tioxide Europ Sas | Magnesium sulphate |
| CN102951947B (en) * | 2012-10-18 | 2014-04-23 | 陕西比迪欧化工有限公司 | System and method for recycling and utilizing waste sulfuric acid to produce phosphate and compound fertilizer |
| CN103496779A (en) * | 2013-10-14 | 2014-01-08 | 铜陵化学工业集团有限公司 | Method for using magniferous ore to treat titanium white acid wastewater |
| CN104118893B (en) * | 2014-07-31 | 2015-11-18 | 四川龙蟒钛业股份有限公司 | One utilizes titanium white waste acid manufacture level magnesium sulfate method |
| CN108751236A (en) * | 2018-06-21 | 2018-11-06 | 山东道恩钛业有限公司 | A kind of method that titanium white waste acid produces fertiliser containing magnesium |
| CN111017968A (en) * | 2019-12-27 | 2020-04-17 | 河北邢台冶金镁业有限公司 | Method for preparing pure magnesium sulfate by using light burned bitter soil as raw material without adding any impurity removing agent |
| CN112159016A (en) * | 2020-09-16 | 2021-01-01 | 内蒙古格林特制药有限责任公司 | Method for recovering and treating waste acid water generated in amantadine synthesis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153140A (en) * | 1995-12-29 | 1997-07-02 | 武汉市环境保护局 | Method for producing potassium sulfate, iron protocarbonate and compound fertilizer using waste acid liquor from titanium pigment plant |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153140A (en) * | 1995-12-29 | 1997-07-02 | 武汉市环境保护局 | Method for producing potassium sulfate, iron protocarbonate and compound fertilizer using waste acid liquor from titanium pigment plant |
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