CN102701153B - Treatment method for titanium dioxide process waste acid generated by molten salt chlorination process - Google Patents
Treatment method for titanium dioxide process waste acid generated by molten salt chlorination process Download PDFInfo
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Abstract
The invention discloses a treatment method for titanium dioxide process waste acid generated by a molten salt chlorination process. The technical scheme adopted by the invention is that the treatment method comprises the following steps of: adopting the titanium dioxide waste acid generated by the molten salt chlorination process as a raw material, filtering to remove solid impurities and obtain filtrate; carrying out aeration treatment on the filtrate by adopting a mode of introducing compressed air or oxygen gas or quickly stirring; removing sulfate radical by using barium chloride solution and enabling the solution subjected to sulfate radical removal to pass through iron-removing resin to obtain a hydrochloric acid solution containing titanium; adding phosphoric acid solution in the hydrochloric acid solution containing titanium to obtain a solid-liquid mixture; filtering for solid-liquid separation, wherein the obtained liquid phase is HCL solution; and washing the obtained solid phase with deionized water and drying to obtain titanium phosphate. According to the treatment method, hydrochloric acid and titanium element in the waste acid can be effectively recycled; the recycled hydrochloric acid can be directly used as hydrochloric acid for coating in the post treatment process of titanium dioxide generated by the chlorination process or can be directly used for a washing liquid of enterprises such as power plants to replace industrial hydrochloric acid; and the generated titanium phosphate can be used as white pigment or flame retardant, and thus the waste of resources and the pollution to the environment are avoided.
Description
Technical field
The present invention relates to a kind for the treatment of process of fused salt chlorimation method titanium dioxide technique spent acid.
Background technology
At present, titanium white production mainly contains chlorination process and two kinds of production technique of sulfuric acid process, fused salt chlorimation method has for sulfuric acid process that technical process is short, level of automation is high, byproduct few (only for sulfuric acid process 1/10), pollute little, more easily obtain the advantages such as high quality rutile type, occupy the dominant position of titanium powder industry.But adopt 1 ton of titanium dioxide of the every production of fused salt chlorimation method will produce 0.55～0.65 ton of spent acid, in its spent acid, contain 25～30%HCl, 1.5～2.5% titanium elements, and 5～6% SO
4 2-, Fe element and Si element.The treatment process of this kind of spent acid is lime neutralisation normally, utilizes carbide slag or lime powder etc. mainly containing alkaline matter and the spent acid of calcium hydroxide, to carry out the rear landfill of acid-base neutralisation processing, causes the wasting of resources, and environment structure is polluted.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind for the treatment of process of fused salt chlorimation method titanium pigment waste acid, and the method can be recycled the hydrochloric acid in spent acid and titanium elements effectively, avoids the waste of resource and the pollution of environment.
Technical solution of the present invention is:
A treatment process for fused salt chlorimation method titanium pigment waste acid, its special character is:
1, get fused salt chlorimation method titanium pigment waste acid as raw material, cross filtering solid impurity and obtain filtrate;
2, filtrate is carried out to Air Exposure 0.5h～1.5h, described Air Exposure is to adopt to pass into pressurized air or pass into oxygen or the mode of rapid stirring;
3, with barium chloride solution, remove sulfate radical in the solution after Air Exposure;
4, by removing the solution of sulfate radical by deironing resin, obtain the hydrochloric acid soln of titaniferous;
5, at 20 ℃～60 ℃, speed with 9g/h～30g/h adds phosphoric acid solution, and in the hydrochloric acid soln of phosphoric acid and described titaniferous, titanium elements amount of substance, than being 0.8:1～1:1, obtains solidliquid mixture, solid-liquid separation is carried out in filtration, and the liquid phase obtaining is HCl solution;
6, filter the solid phase process deionized water wash obtaining to filtrate pH=4～5, constant temperature drying 7h～9h at 90 ℃～100 ℃, obtains titanium phosphate.
Above-mentioned Air Exposure is the mode by rapid stirring.
Above-mentioned while removing in the solution after Air Exposure sulfate radical with barium chloride solution, bariumchloride with the amount of substance of described sulfate radical than being 1:1.
The present invention only needs filtration, aeration and simple chemical treatment, and technological operation is simple, can suitability for industrialized production; The hydrochloric acid reclaiming hydrochloric acid used can be directly used in chloride process titanium dioxide aftertreatment technology coating time, also can be directly used in the washing lotion of the enterprises such as power plant, substitutes technical-grade hydrochloric acid; The titanium phosphate generating can be used as white pigment and is used to the fields such as dyestuff, leather, also can be used as fire retardant application.
Embodiment
Embodiment 1
Get fused salt chlorimation method titanium white waste acid 400g, cross filtering solid impurity and obtain filtrate, adopt the mode of rapid stirring to carry out Air Exposure 0.5h filtrate; According to sulfate radical in the solution after Air Exposure and bariumchloride amount of substance, be 1:1, by the disposable solution adding after Air Exposure of 50% barium chloride solution 8.6g, stir 20min, filter and remove barium sulfate precipitate; To remove the solution of sulfate radical by deironing resin, obtain the hydrochloric acid soln of titaniferous 3%, at 60 ℃, speed with 0.5g/min adds phosphoric acid solution, in the hydrochloric acid soln of the add-on of phosphoric acid solution and described titaniferous, titanium elements amount of substance is than being 0.8:1, obtain solidliquid mixture, filter and carry out solid-liquid separation, the liquid phase obtaining is HCl solution; The solid phase obtaining to filtrate pH=4, is dried 8h by solid product after washing with deionized water wash in 90 ℃ of constant temperature ovens, obtains titanium phosphate.
Embodiment 2
Get fused salt chlorimation method titanium white waste acid 300g, cross filtering solid impurity and obtain filtrate, filtrate employing is passed into compressed-air actuated mode and carry out Air Exposure 1h; According to sulfate radical in the solution after Air Exposure and bariumchloride amount of substance, be 1:1, by the disposable solution adding after Air Exposure of 50% barium chloride solution 6.4g, stir 20min, filter and remove barium sulfate precipitate; To remove the solution of sulfate radical by deironing resin, obtain the hydrochloric acid soln of titaniferous 2.9%, at 40 ℃, speed with 0.3g/min adds phosphoric acid solution, in the hydrochloric acid soln of the add-on of phosphoric acid solution and described titaniferous, titanium elements amount of substance is than being 0.9:1, obtain solidliquid mixture, filter and carry out solid-liquid separation, the liquid phase obtaining is HCl solution; The solid phase obtaining to filtrate pH=4.5, is dried 7h by solid product after washing with deionized water wash in 90 ℃ of constant temperature ovens, obtains titanium phosphate.
Embodiment 3
Get fused salt chlorimation method titanium white waste acid 200g, cross filtering solid impurity and obtain filtrate, the mode that filtrate employing is passed into oxygen is carried out Air Exposure 1.5h; According to sulfate radical in the solution after Air Exposure and bariumchloride amount of substance, be 1:1, by the disposable solution adding after Air Exposure of 50% barium chloride solution 4.3g, stir 20min, filter and remove barium sulfate precipitate; To remove the solution of sulfate radical by deironing resin, obtain the hydrochloric acid soln of titaniferous 3.2%, at 20 ℃, with the speed of 0.15g/min add with the hydrochloric acid soln of described titaniferous in the equimolar phosphoric acid solution of titanium elements, obtain solidliquid mixture, solid-liquid separation is carried out in filtration, and the liquid phase obtaining is HCl solution; The solid phase obtaining to filtrate pH=5, is dried 9h by solid product after washing with deionized water wash in 100 ℃ of constant temperature ovens, obtains titanium phosphate.
Product sampling analysis result in above-described embodiment is as shown in the table:
Claims (3)
1. a treatment process for fused salt chlorimation method titanium pigment waste acid, is characterized in that:
1.1 get fused salt chlorimation method titanium pigment waste acid as raw material, cross filtering solid impurity and obtain filtrate;
1.2 carry out Air Exposure 0.5h～1.5h by filtrate, and described Air Exposure is to adopt to pass into pressurized air or pass into oxygen or the mode of rapid stirring;
1.3 use barium chloride solutions are removed sulfate radical in the solution after Air Exposure;
1.4 by removing the solution of sulfate radical by deironing resin, obtains the hydrochloric acid soln of titaniferous;
1.5 at 20 ℃～60 ℃, speed with 9g/h～30g/h adds phosphoric acid solution, and in the hydrochloric acid soln of phosphoric acid solution and described titaniferous, titanium elements amount of substance, than being 0.8:1～1:1, obtains solidliquid mixture, solid-liquid separation is carried out in filtration, and the liquid phase obtaining is HCl solution;
1.6 filter the solid phase process deionized water wash obtaining to filtrate pH=4～5, and constant temperature drying 7h～9h at 90 ℃～100 ℃, obtains titanium phosphate.
2. the treatment process of fused salt chlorimation method titanium pigment waste acid according to claim 1, is characterized in that: described Air Exposure is the mode by rapid stirring.
3. the treatment process of fused salt chlorimation method titanium pigment waste acid according to claim 1, is characterized in that: bariumchloride is 1:1 with the amount of substance ratio of described sulfate radical.
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| CN103447283B (en) * | 2013-08-30 | 2017-06-09 | 漯河兴茂钛业股份有限公司 | The Safe disposal method of waste residue produced by Titanium Dioxide Produced by Chloride Procedure production titanium tetrachloride |
| CN103432867A (en) * | 2013-08-30 | 2013-12-11 | 漯河兴茂钛业股份有限公司 | Method for comprehensively utilizing waste hydrochloric acid produced in chlorination eluting tail gas process in chlorination method titanium white production |
| CN103934010B (en) * | 2014-04-01 | 2015-10-28 | 河南师范大学 | The preparation method of diverse microcosmic appearance bismuth phosphate photocatalyst |
| CN109795989A (en) * | 2019-01-16 | 2019-05-24 | 东南大学 | A method of it obtaining hydrochloride aqueous solution from the hydrogen chloride solution of sulfur-bearing and prepares alkali salt hydrochlorate |
| CN112386962A (en) * | 2020-11-26 | 2021-02-23 | 河南佰利联新材料有限公司 | Method for increasing sedimentation velocity of thickening tank |
| CN113371750B (en) * | 2021-06-08 | 2023-07-28 | 龙佰集团股份有限公司 | Method for preparing barium sulfate by combining titanium white waste acid with chlorination method and titanium white waste acid with sulfuric acid method |
| CN115231540A (en) * | 2022-08-05 | 2022-10-25 | 山东鲁北国际新材料研究院有限公司 | Method for preparing titanium phosphate from byproduct waste acid generated in titanium dioxide production by chlorination process |
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Address after: 121000 Jin Ti Road 1, Taihe District, Jinzhou, Liaoning Patentee after: Jinzhou titanium Limited by Share Ltd Address before: 121000 alloy Li 59, Taihe District, Liaoning, Jinzhou Patentee before: Jinzhou Titanium Industry Co., Ltd. |
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Address after: 121000 Kam Ti Road, Taihe District, Jinzhou, Liaoning Province, No. 1 Patentee after: CITIC titanium Limited by Share Ltd Address before: 121000 Kam Ti Road, Taihe District, Jinzhou, Liaoning Province, No. 1 Patentee before: Jinzhou titanium Limited by Share Ltd |