CN103058253A - Method for preparing gypsum by free sulfuric acid in titanium dioxide wastewater - Google Patents
Method for preparing gypsum by free sulfuric acid in titanium dioxide wastewater Download PDFInfo
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- CN103058253A CN103058253A CN2013100197405A CN201310019740A CN103058253A CN 103058253 A CN103058253 A CN 103058253A CN 2013100197405 A CN2013100197405 A CN 2013100197405A CN 201310019740 A CN201310019740 A CN 201310019740A CN 103058253 A CN103058253 A CN 103058253A
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Abstract
The invention discloses a method for preparing gypsum by free sulfuric acid in titanium dioxide wastewater. The method comprises the following steps of: a: collecting acidic wastewater produced by a sulfuric acid method in a production process of titanium dioxide in an adjusting tank; b: transporting the acidic wastewater in the adjusting tank into a reaction tank, and at the same time, adding limestone mineral powder slurry ground by grinding equipment in the reaction tank to neutralize free sulfuric acid; c: transporting the prepared gypsum slurry into a precipitation tank, and fully dehydrating to prepare crude gypsum; d: washing the prepared crude gypsum with a little clean water, and finally washing with a little lime milk solution; and e: secondarily squeezing the washed crude gypsum and fully dehydrating to prepare the gypsum product. The method has the beneficial effects that the gypsum is prepared by free sulfuric acid in the wastewater, stable emission standard of the wastewater can be guaranteed, and solid slag produced by the sulfuric acid method in a wastewater processing technology of titanium dioxide becomes treasure from waste, so that in the whole processing process, the output of solid waste is greatly reduced, and therefore, the cost of wastewater processing is greatly reduced.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of industrial waste, be specifically related to a kind of method of utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum.
Background technology
In the sulfate process titanium dioxide production technique, 1 ton of titanium dioxide of every production can produce the dilute sulphuric acid of 5-6 ton 20%-25% concentration.In addition, the acid waste water that 1 ton of titanium dioxide of every production produces in process of production comprises acid hydrolysis tail gas washing water, calcining washing tail gas water, washing waste water, equipment wash-down water and a ground flushing water, and its generation is 50-80m
3(about sulfuric acid content 2%, containing a small amount of ferrous sulfate and titanium dioxide), caused serious environmental pollution, and wasted a large amount of available resources.At present, being treated to that the waste water that produces in the sulfuric acid method titanium pigment production technique adopts uses alkaline precipitating agent lime, carbide slag etc. with after the acid waste water neutralization, precipitating, and standard emission of clear has produced a large amount of body refuses after the precipitated product press filtration.
The solid waste that this method produces need be stacked, not only spent a large amount of in and cost but also consume a large amount of soils and stack waste residues, body refuse landfill expense accounts for 20% of cost of sewage disposal in the running cost, the body refuse that produces after administering, do not have utility value, carry out landfill disposal as inorganic refuse.This needs very large area slag field, not only wastes land resources, and can produce very large pollution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method of utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum, thus pollution abatement, and utilize in the spent acid available resource to produce useful product.
For achieving the above object, technical scheme of the present invention is as follows: a kind of method of utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum may further comprise the steps:
A, the acid waste water that produces in the sulfuric acid method titanium pigment production process is collected equalizing tank, Controlled acidity is between 2-5%;
B, the acid waste water in the equalizing tank is conveyed into reactive tank, add in the reactive tank simultaneously by in the Wingdale of abrasive dust equipment milled or calcium oxide or the calcium hydroxide mineral powder slurry and free sulfuric acid, and stir by whipping device and fully to react, reaction times is 60-90 minute, make gypsum slurries, the pH value of gypsum slurries is 1-3;
C, the gypsum slurries that makes is transported to settling bath, the noncorrosive pump by the settling bath bottom is transported to dehydration equipment with gypsum slurries, fully makes rubble cream after the dehydration, supernatant liquor and filtrate enter Sewage treatment systems process after qualified discharge;
D, the rubble cream that makes is washed with a small amount of clear water, wash with a small amount of lime milk solution at last;
E, the rubble cream after will washing carry out twice pressing and fully dewater, and make gypsum product, and the discharging press filtration becomes gypsum filter cake.
Preferably, described Wingdale or calcium oxide or calcium hydroxide ore powder granularity are the 100-300 order, and purity is more than 95%.
Preferably, the free water content in the rubble cream product that Dehydration gets among the described step c≤25%, the gypsum contents on dry basis is not less than 90% in the filter cake among the described step e after the discharging press filtration.
Preferably, the lime milk solution pH value is 10-13 in the described steps d, and described lime milk solution wash filtrate pH value is 6-9, makes gypsum and is neutral.
Preferably, the reactive tank among the described step b is anticorrosion Reinforced Concrete Structure, is provided with three reaction zones, is equipped with whipping device in described three reaction zones.
Preferably, the abrasive dust equipment among the described step b is ball mill.
Preferably, the whipping device among the described step b is machine mixer.
Preferably, the dehydration equipment among the described step c is diaphragm filter press and corrosion-resistant filter pressing pump.
Adopt the beneficial effect of above technical scheme to be: to utilize the free sulfuric acid in the titanium dioxide wastewater to produce the stably reaching standard discharging that gypsum can not only guarantee waste water, the solid slag that produces in the sulfuric acid method titanium pigment waste water treatment process is turned waste into wealth, greatly reduce the generation of solid waste in the whole treating processes, thereby greatly reduced the cost of wastewater treatment.
Embodiment
The below will be clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
Embodiment 1
A kind of method of utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum may further comprise the steps:
A, the acid waste water that produces in the sulfuric acid method titanium pigment production process is collected equalizing tank, Controlled acidity is between 2-5%;
B, with the acid waste water in the equalizing tank with 400m
3The speed of/h is conveyed into reactive tank, reactive tank is Reinforced Concrete Structure, be provided with three reaction zones, add in the reactive tank simultaneously by in the limestone dust slurries of abrasive dust equipment milled and free sulfuric acid, used abrasive dust equipment is ball mill, the fineness of limestone dust is 100 orders, and purity is equipped with whipping device more than 95% in three reaction zones, whipping device is machine mixer, stirring velocity is 80r/min, stirs by machine mixer, fully reacts in three reaction zones, reaction times is 60-90 minute, make gypsum slurries, the pH value of gypsum slurries is 1-3, with 440m
3The load of/h is kept liquid level stabilizing in the reactive tank;
C, the gypsum slurries that makes is transported to settling bath, noncorrosive pump by the settling bath bottom is transported to dehydration equipment with gypsum slurries, dehydration equipment is diaphragm filter press and corrosion-resistant filter pressing pump, fully make rubble cream after the dehydration, free water content in the rubble cream≤25%, supernatant liquor and filtrate enter Sewage treatment systems and process rear qualified discharge;
D, the rubble cream that makes is washed with a small amount of clear water, reduce carrying secretly of harmful element Fe, wash with a small amount of lime milk solution at last, the lime milk solution pH value is 10-13, and lime milk solution wash filtrate pH value is 6-9, makes gypsum and is neutrality;
E, the rubble cream after will washing carry out twice pressing and fully dewater, and make gypsum product, and the discharging press filtration becomes gypsum filter cake, and the gypsum contents on dry basis is not less than 90% in the filter cake after the discharging press filtration.
Embodiment 2
All the other are identical with embodiment 1, and difference is that the fineness of described limestone dust is 200 orders.
Embodiment 3
All the other are identical with embodiment 1, and difference is that the fineness of described limestone dust is 300 orders.
Embodiment 4
All the other are identical with embodiment 1, and difference is, add in the reactive tank by in the calcium oxide mineral powder slurry of abrasive dust equipment milled and free sulfuric acid.
Embodiment 5
All the other are identical with embodiment 1, and difference is, add in the reactive tank by in the calcium hydroxide mineral powder slurry of abrasive dust equipment milled and free sulfuric acid.
Utilize the free sulfuric acid in the titanium dioxide wastewater to produce the stably reaching standard discharging that gypsum can not only guarantee waste water, the solid slag that produces in the sulfuric acid method titanium pigment waste water treatment process is turned waste into wealth, greatly reduce the generation of solid waste in the whole treating processes, thereby greatly reduced the cost of wastewater treatment.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a method of utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum is characterized in that, may further comprise the steps:
A, the acid waste water that produces in the sulfuric acid method titanium pigment production process is collected equalizing tank, Controlled acidity is between 2-5%;
B, the acid waste water in the equalizing tank is conveyed into reactive tank, add in the reactive tank simultaneously by in the Wingdale of abrasive dust equipment milled or calcium oxide or the calcium hydroxide mineral powder slurry and free sulfuric acid, and stir by whipping device and fully to react, reaction times is 60-90 minute, make gypsum slurries, the pH value of gypsum slurries is 1-3;
C, the gypsum slurries that makes is transported to settling bath, the noncorrosive pump by the settling bath bottom is transported to dehydration equipment with gypsum slurries, fully makes rubble cream after the dehydration, supernatant liquor and filtrate enter Sewage treatment systems process after qualified discharge;
D, the rubble cream that makes is washed with a small amount of clear water, wash with a small amount of lime milk solution at last;
E, the rubble cream after will washing carry out twice pressing and fully dewater, and make gypsum product, and the discharging press filtration becomes gypsum filter cake.
2. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, described Wingdale or calcium oxide or calcium hydroxide ore powder granularity are the 100-300 order, and purity is more than 95%.
3. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1, it is characterized in that, free water content in the rubble cream product that Dehydration gets among the described step c≤25%, the gypsum contents on dry basis is not less than 90% in the filter cake among the described step e after the discharging press filtration.
4. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, the lime milk solution pH value is 10-13 in the described steps d, and described lime milk solution wash filtrate pH value is 6-9, makes gypsum and is neutral.
5. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, the reactive tank among the described step b is anticorrosion Reinforced Concrete Structure, is provided with three reaction zones, is equipped with whipping device in described three reaction zones.
6. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, the abrasive dust equipment among the described step b is ball mill.
7. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, the whipping device among the described step b is machine mixer.
8. the method for utilizing the titanium dioxide wastewater Free Sulfuric Acid to produce gypsum according to claim 1 is characterized in that, the dehydration equipment among the described step c is diaphragm filter press and corrosion-resistant filter pressing pump.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395816A (en) * | 2013-07-22 | 2013-11-20 | 蓝星（成都）新材料有限公司 | Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle |
| CN103693727A (en) * | 2013-12-18 | 2014-04-02 | 山东国大黄金股份有限公司 | Method for sewage neutralization and efficient cyclic utilization of waste residue |
| CN105236777A (en) * | 2015-09-02 | 2016-01-13 | 富民龙腾钛业有限责任公司 | Method of producing white gypsum used for building materials by means of titanium dioxide waste acid |
| CN105439483A (en) * | 2014-09-26 | 2016-03-30 | 河南佰利联化学股份有限公司 | Method for producing low-water-content white titanium gypsum |
| CN105502980A (en) * | 2014-09-26 | 2016-04-20 | 河南佰利联化学股份有限公司 | Industrial production process for white titanium gypsum with low water content |
| CN105985037A (en) * | 2015-03-17 | 2016-10-05 | 住友大阪水泥株式会社 | Method of producing gypsum and method of producing cement composition |
| CN106380018A (en) * | 2016-10-10 | 2017-02-08 | 华南理工大学 | Titanium dioxide wastewater treatment method favorable for improving utilization ratio of calcium oxide and dehydration property of byproduct gypsum |
| CN107445192A (en) * | 2017-07-24 | 2017-12-08 | 广西藤县广峰钛白有限公司 | The recoverying and utilizing method and its equipment of titanium powder plant discarded object GYPSUM RUBRUM |
| CN109179476A (en) * | 2018-09-04 | 2019-01-11 | 铜陵化学工业集团有限公司 | A method of control titanium gypsum water content |
| CN111116069A (en) * | 2019-12-26 | 2020-05-08 | 安徽迪诺环保新材料科技有限公司 | Fabricated building wall, titanium gypsum used by fabricated building wall and preparation method of titanium gypsum |
| CN111348670A (en) * | 2020-03-13 | 2020-06-30 | 江苏一夫科技股份有限公司 | Method for preparing titanium gypsum from titanium white waste acid |
| CN111960700A (en) * | 2020-07-16 | 2020-11-20 | 云锡文山锌铟冶炼有限公司 | Method for comprehensively utilizing waste water containing dilute sulfuric acid |
| CN112441676A (en) * | 2019-09-02 | 2021-03-05 | 攀枝花大互通钛业有限公司 | Method for treating acid wastewater of titanium dioxide by sulfuric acid process |
| WO2022104737A1 (en) * | 2020-11-20 | 2022-05-27 | 成都千砺金科技创新有限公司 | Production method for full resource recycling of wastewater from sulfuric-acid-method-based titanium dioxide production |
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Cited By (20)
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| CN103395816B (en) * | 2013-07-22 | 2015-04-22 | 蓝星（成都）新材料有限公司 | Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle |
| CN103395816A (en) * | 2013-07-22 | 2013-11-20 | 蓝星（成都）新材料有限公司 | Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle |
| CN103693727A (en) * | 2013-12-18 | 2014-04-02 | 山东国大黄金股份有限公司 | Method for sewage neutralization and efficient cyclic utilization of waste residue |
| CN103693727B (en) * | 2013-12-18 | 2015-05-13 | 山东国大黄金股份有限公司 | Method for sewage neutralization and efficient cyclic utilization of waste residue |
| CN105439483A (en) * | 2014-09-26 | 2016-03-30 | 河南佰利联化学股份有限公司 | Method for producing low-water-content white titanium gypsum |
| CN105502980A (en) * | 2014-09-26 | 2016-04-20 | 河南佰利联化学股份有限公司 | Industrial production process for white titanium gypsum with low water content |
| CN105985037A (en) * | 2015-03-17 | 2016-10-05 | 住友大阪水泥株式会社 | Method of producing gypsum and method of producing cement composition |
| CN105236777A (en) * | 2015-09-02 | 2016-01-13 | 富民龙腾钛业有限责任公司 | Method of producing white gypsum used for building materials by means of titanium dioxide waste acid |
| CN106380018B (en) * | 2016-10-10 | 2019-08-20 | 华南理工大学 | A kind of titanium dioxide wastewater processing method for being conducive to improve oxidation calcium utilization and by-product gypsum dewatering |
| CN106380018A (en) * | 2016-10-10 | 2017-02-08 | 华南理工大学 | Titanium dioxide wastewater treatment method favorable for improving utilization ratio of calcium oxide and dehydration property of byproduct gypsum |
| CN107445192A (en) * | 2017-07-24 | 2017-12-08 | 广西藤县广峰钛白有限公司 | The recoverying and utilizing method and its equipment of titanium powder plant discarded object GYPSUM RUBRUM |
| CN109179476A (en) * | 2018-09-04 | 2019-01-11 | 铜陵化学工业集团有限公司 | A method of control titanium gypsum water content |
| CN109179476B (en) * | 2018-09-04 | 2021-10-26 | 铜陵化学工业集团有限公司 | Method for controlling water content of titanium gypsum |
| CN112441676A (en) * | 2019-09-02 | 2021-03-05 | 攀枝花大互通钛业有限公司 | Method for treating acid wastewater of titanium dioxide by sulfuric acid process |
| CN111116069A (en) * | 2019-12-26 | 2020-05-08 | 安徽迪诺环保新材料科技有限公司 | Fabricated building wall, titanium gypsum used by fabricated building wall and preparation method of titanium gypsum |
| CN111116069B (en) * | 2019-12-26 | 2022-02-01 | 安徽迪诺环保新材料科技有限公司 | Fabricated building wall, titanium gypsum used by fabricated building wall and preparation method of titanium gypsum |
| CN111348670A (en) * | 2020-03-13 | 2020-06-30 | 江苏一夫科技股份有限公司 | Method for preparing titanium gypsum from titanium white waste acid |
| CN111960700A (en) * | 2020-07-16 | 2020-11-20 | 云锡文山锌铟冶炼有限公司 | Method for comprehensively utilizing waste water containing dilute sulfuric acid |
| WO2022104737A1 (en) * | 2020-11-20 | 2022-05-27 | 成都千砺金科技创新有限公司 | Production method for full resource recycling of wastewater from sulfuric-acid-method-based titanium dioxide production |
| JP2023509228A (en) * | 2020-11-20 | 2023-03-07 | 成都千砺金科技創新有限公司 | Complete resource recycling method for wastewater from sulfuric acid titanium white production |
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Application publication date: 20130424 |