CN103540751A - Method for treating titanium tetrachloride refining tailings - Google Patents
Method for treating titanium tetrachloride refining tailings Download PDFInfo
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- CN103540751A CN103540751A CN201310475987.8A CN201310475987A CN103540751A CN 103540751 A CN103540751 A CN 103540751A CN 201310475987 A CN201310475987 A CN 201310475987A CN 103540751 A CN103540751 A CN 103540751A
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- titanium tetrachloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the field of chemical engineering and relates to a method for treating titanium tetrachloride refining tailings. The method comprises the following steps of carrying out neutralization chlorine-fixation treatment on titanium tetrachloride refining tailings as base raw materials by a calcium oxide aqueous solution to leach calcium chloride and aluminum chloride, carrying out solid-liquid separation to obtain filter cake and a filtrate, carrying out clarification on the filtrate to separate suspended solids and to obtain a clear aqueous solution, and drying the filter cake. The method realizes green treatment on the titanium tetrachloride refining tailings. The filter cake obtained by the method can be used as a raw material of vanadium alloy smelting and the aqueous solution obtained by the method can be used for removal of phosphor and silicon in the solution.
Description
Technical field
The invention belongs to titanium chemical field, be specifically related to the treatment process of the refining tailings of a kind of titanium tetrachloride.
Background technology
The refining tailings of titanium tetrachloride is that chlorination process is produced the waste residue producing with aluminium powder refining crude titanium tetrachloride vanadium removal in titanium tetrachloride process, and main component is: 4%V, 4.2%Fe, 22.2%Al, 4.5%Ti, 1.5%Ca, 0.5%Na, 0.4%K; Except these compositions, in this slag, the maximum chlorine in addition of content, has brought a series of environmental influences just because of its existence, and this waste residue is that titanium tetrachloride is produced one of most typical solid waste.
At present, the processing of this waste is all almost to use lime neutralisation, residue after neutralization nearly all adopts to be stored up or landfill is disposed, because the refining tailings of titanium tetrachloride can discharge a large amount of chlorine in the process of storing up, environmental pollution is serious, because content of vanadium in slag is higher, also caused certain wasting of resources simultaneously.Therefore present method of disposal does not fundamentally solve environmental issue, has environmental safety hidden danger.
Chinese invention patent ZL200710202250.3 discloses recovery method and the equipment containing vanadium mud producing in a kind of titanium tetrachloride refining process, and the method is carried out in two steps: the first step is converted into dichloro vanadyl by vanadium oxytrichloride; Second step is that the mud that contains dichloro vanadyl is sprayed in chlorination system, and the temperature spraying into is a little controlled at 150 ℃～190 ℃.The object of this invention is just for the titanium tetrachloride in separated mud more effectively, do not relate to the problems such as recycling, environment protection treating of vanadium.
Chinese invention patent ZL02132626.6 discloses a kind of titanium tetrachloride treatment of mud method and apparatus containing vanadium, it be the device that utilizes former chlorination system with heat energy to crude titanic chloride mineral oil except in vanadium operation, discharge containing the titanium tetrachloride in vanadium mud with containing vanadium solid, carry out separated technology, still do not relate to the problems such as vanadium, environment protection treating.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the treatment process of the refining tailings of a kind of titanium tetrachloride.It is basic raw material that the method be take the refining tailings of titanium tetrachloride, adopting calcium oxide aqueous solution to neutralize solid chlorine processes, after solid-liquid separation, obtain two kinds of materials of filter cake and filtrate, filtrate has obtained the aqueous solution of clarification after clarified separation suspended substance, thereby has completed the greenization processing of the refining tailings of titanium tetrachloride.
First technical problem to be solved by this invention is to provide the treatment process of the refining tailings of a kind of titanium tetrachloride.The method comprises the following steps:
A, neutralization: calcium lime powder, water, the refining tailings of titanium tetrachloride are mixed, and control mixing speed is 300r/min～600r/min, and churning time is 20min～60min, and controlling pH value is 8～10, obtains calcic slag slurry;
B, separation: separated calcic slag slurry, obtains filter cake and filtrate;
C, aftertreatment: by removing suspended substance after the filtrate clarification of step b gained, obtain the aqueous solution of clarification.
Specifically, above-mentioned treatment process, the refining tailings of described titanium tetrachloride refers to that the crude titanic chloride that chlorination process is produced adopts metallic aluminium to refine, then evaporation concentration reclaims the solids after titanium tetrachloride, can be both filter cake, can be also the mud after concentrating.
Preferably, above-mentioned treatment process, in step a, in described calcium lime powder, calcium oxide content is more than 75%wt, and calcium lime powder granularity is no more than 0.1mm.
Preferably, above-mentioned treatment process, in step a, described calcic screenings pH value is 9.
Preferably, above-mentioned treatment process, in step a, counts ， Shui ︰ tailings=1～4 ︰ 1 in mass ratio.
Further, preferred, above-mentioned treatment process, in step a, counts ， Shui ︰ tailings=1～3 ︰ 1 in mass ratio.
Preferably, above-mentioned treatment process, in step a, described churning time is 30min～40min.
Preferably, above-mentioned treatment process, in step a, described mixing speed is 350r/min～450r/min.
Second Problem to be solved by this invention is to provide by the preparation-obtained filter cake of above-mentioned treatment process.
The present invention provides the purposes of above-mentioned filter cake as vanadium alloy raw materials for metallurgy simultaneously.
The 3rd problem to be solved by this invention is to provide the preparation-obtained aqueous solution in above-mentioned process method step c.
The present invention provides the purposes of the above-mentioned aqueous solution as phosphorus, silicon composite purifying agent simultaneously.
Titanium tetrachloride of the present invention is refined tailings treatment process, has fundamentally solved the environmental safety hidden danger of the refining tailings of titanium tetrachloride, has realized to greatest extent the recycling of the refining tailings of titanium tetrachloride, has good environmental benefit and economic benefit; And the method production technique is simple, and element recovery rate is high, and production cost is low, there is no new three wastes output, belong to green treatment process; And gained filter cake can be used as vanadium alloy raw materials for metallurgy after finishing dealing with, the aqueous solution of gained clarification can be used as phosphorus, silicon composite purifying agent, has good economic benefit.
Embodiment
A refining tailings treatment process, comprises the following steps:
A, neutralization: calcium lime powder, water, the refining tailings of titanium tetrachloride are mixed, and control mixing speed is 300r/min～600r/min, and churning time is 20min～60min, and controlling pH value is 8～10, obtains calcic slag slurry;
B, separation: separated calcic slag slurry, obtains filter cake and filtrate;
C, aftertreatment: by removing suspended substance after the filtrate clarification of step b gained, obtain the aqueous solution of clarification.
In treating processes, the filter cake that separation obtains can adopt water washing, the filtration cakes torrefaction after washing, and gained washings can be mixed in filtrate; Suspended substance in filtrate also can be mixed in filter cake, thereby raw material is utilized more fully.
The refining tailings of titanium tetrachloride of the present invention refers to that the crude titanic chloride that chlorination process is produced adopts metallic aluminium to refine, and then evaporation concentration reclaims the solids after titanium tetrachloride, can be both filter cake, can be also the mud after concentrating.Through research, find, adopting unslaked lime is that raw material neutralizes refining tailings, not only effective, and easy to operate; Find simultaneously, in unslaked lime the content of calcium oxide more than 75wt%, calcium oxide content low also can, just add-on is wanted greatly, to be inconvenient to operate.
In fact the refining tailings of calcium oxide neutralization titanium tetrachloride also can react under anhydrous condition, for no other reason than that the homogeneity of reaction is poor, corrodibility is more outstanding, the escape meeting of chlorine is more, on the impact of environmental protection, will show, in addition, what anhydrous response obtained is the mixture of solid, water miscible aluminum chloride, calcium chloride can not be separated with solid residue, can not carry out recycling, still can become environmental pressure, so the present invention preferably adopts and reacts having under the condition of water.Meanwhile, the operation of the refining tailings of calcium oxide neutralization titanium tetrachloride both can be carried out in titanium tetrachloride output zone, also can carry out in strange land; Consider the impact on environment, the operation of calcium oxide neutralization tailings is chosen in titanium tetrachloride output zone and carries out as good.
The object that the present invention controls pH has two, and the firstth, for solid chlorine, and avoid chlorine escape contaminate environment; The secondth, in and chlorine, allow whole solution in mild state, avoid the serious problems such as corrosion; PH is controlled to 8～10, is on the one hand for chlorine fully admittedly, and avoid on the other hand causing, unslaked lime consumption is excessive wastes.The present invention regulates pH value by the ratio of refining tailings and unslaked lime, can add refining tailings and unslaked lime according to actually operating, only needs to guarantee pH to be controlled at 8～10.
The present invention controls the concentration of calcium chloride, aluminum chloride in the principal defecation aqueous solution by adding water, can according to difference need to decide add water number.Further, in order to lower the viscosity of solution, water and tailings mass ratio can be controlled to 1～4 ︰ 1, be preferably 1～3 ︰ 1, the inventive method can disposablely add water, also can add at twice water, no matter be which kind of situation, pH is controlled at the pH-value that will control the most at last.
The treatment process of the refining tailings of this titanium tetrachloride, complete, abundant by selecting above-mentioned suitable pH value, reaction times and stirring intensity not only to guarantee economically that reaction is carried out, and have and fundamentally solve the potential safety hazard of this tailings, realized recycling to greatest extent, have good environmental benefit and economic benefit, this method production technique is simple, element yield is high, production cost is low.The method is to process at present the refining more applicable method of tailings of titanium tetrachloride.
In the inventive method, the method for separated calcic slag slurry is a lot, can adopt the ripe technique of conventional suction filtration (suction strainer), press filtration etc.
In the resulting filter cake of the present invention, contain elemental vanadium, can be used as vanadium alloy raw materials for metallurgy; Gained clear aqueous solution can be used for being used as phosphorus, silica purge agent in hydrometallurgy industry, is specially adapted to be used as in vanadium oxides producing process purification dephosphorization, the silica removal of sodium vanadate solution.
Not specified in the inventive method, described content is massfraction.
Embodiment 1
Get the refining tailings 100kg of titanium tetrachloride, after testing, its principal element content is: 4%V, 4.2%Fe, 9.7%Al, 4.5%Ti, 1.5%Ca; Unslaked lime is crushed to granularity and is no more than 0.1mm, the calcium oxide content of analyzing is wherein 85.12%.In neutralization tank, add 80 ℃ of clear water 150kg, slowly add unslaked lime 25kg, stirring reaction 40min under the condition of mixing speed 300r/min, the pH value that records solution is 8.35, and slip is squeezed into press filtration in plate-and-frame filter press, obtain filter cake and filtrate, the heavy 28kg of wet cake, the heavy 243kg of filtrate, filtrate continues to squeeze into suction filtration in suction filtration tank after clarification 24h, obtain clear aqueous solution 238kg, get clear aqueous solution analysis, calcium chloride content is 17.2%, and aluminum chloride content is 18.7%.
Embodiment 2
Get the refining tailings 100kg of titanium tetrachloride, after testing, its principal element content is: 4%V, 4.2%Fe, 9.7%Al, 4.5%Ti, 1.5%Ca; Unslaked lime crushing grinding to granularity is no more than to 0.1mm, and the calcium oxide content of analyzing is wherein 85.12%.In neutralization tank, add 60 ℃ of clear water 200kg, slowly add unslaked lime 27kg, stirring reaction 60min under the condition of mixing speed 400r/min, the pH value that records solution is 8.75, and slip is squeezed into press filtration in plate-and-frame filter press, obtain filter cake and filtrate, the heavy 30.5kg of wet cake, the heavy 287kg of filtrate, filtrate continues to squeeze into suction filtration in suction filtration tank after clarification 24h, obtain clear aqueous solution 278kg, get clear aqueous solution analysis, calcium chloride content is 14.7%, and aluminum chloride content is 15.8%.
Embodiment 3
Get the refining tailings 100kg of titanium tetrachloride, after testing, its principal element content is: 4%V, 4.2%Fe, 9.7%Al, 4.5%Ti, 1.5%Ca; Unslaked lime crushing grinding to granularity is no more than to 0.1mm, and the calcium oxide content of analyzing is wherein 85.12%.In neutralization tank, add 40 ℃ of clear water 400kg, slowly add unslaked lime 30kg, stirring reaction 20min under the condition of mixing speed 600r/min, the pH value that records solution is 9.15, and slip is squeezed into press filtration in plate-and-frame filter press, obtain filter cake and filtrate, the heavy 34.5kg of wet cake, the heavy 479kg of filtrate, filtrate continues to squeeze into suction filtration in suction filtration tank after clarification 24h, obtain clear aqueous solution 458kg, get clear aqueous solution analysis, calcium chloride content is 10.6%, and aluminum chloride content is 11.4%.
Claims (10)
1. titanium tetrachloride is refined a treatment process for tailings, it is characterized in that: comprise the following steps:
A, neutralization: calcium lime powder, water, the refining tailings of titanium tetrachloride are mixed, and control mixing speed is 300r/min～600r/min, and churning time is 20min～60min, and controlling pH value is 8～10, obtains calcic slag slurry;
B, separation: separated calcic slag slurry, obtains filter cake and filtrate;
C, aftertreatment: by removing suspended substance after the filtrate clarification of step b gained, obtain the aqueous solution of clarification.
2. treatment process according to claim 1, it is characterized in that: the refining tailings of described titanium tetrachloride refers to that the crude titanic chloride that chlorination process is produced adopts metallic aluminium to refine, then evaporation concentration reclaims the solids after titanium tetrachloride, can be both filter cake, can be also the mud after concentrating.
3. treatment process according to claim 1, is characterized in that: in step a, in calcium lime powder, calcium oxide content is more than 75wt%, and calcium lime powder granularity is no more than 0.1mm.
4. treatment process according to claim 1, is characterized in that: in step a, described calcic screenings pH value is 9.
5. treatment process according to claim 1, is characterized in that: in step a, count in mass ratio ， Shui ︰ tailings=1～4 ︰ 1.
6. treatment process according to claim 1, is characterized in that: in step a, and described mixing speed 350r/min～450r/min, described churning time is 30min～40min.
7. by the preparation-obtained filter cake of claim 1～6 any one treatment process.
Described in claim 7 filter cake as the purposes of vanadium alloy raw materials for metallurgy.
9. preparation-obtained clear aqueous solution in claim 1～6 any one process method step c.
Described in claim 9 clear aqueous solution as the purposes of phosphorus, silicon composite purifying agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834989A (en) * | 2014-02-24 | 2014-06-04 | 锦州钛业有限公司 | Process of producing calcium sulfate crystal whiskers from chloride-containing wastewater generated in chloride process titanium dioxide production |
| CN105107830A (en) * | 2015-09-24 | 2015-12-02 | 云南新立有色金属有限公司 | Method for treating boiling chlorination waste residue |
| CN108372185A (en) * | 2018-04-20 | 2018-08-07 | 江苏久吾高科技股份有限公司 | A kind of titanium chloride slag resource utilization method and its device |
| CN108372185B (en) * | 2018-04-20 | 2024-05-03 | 江苏久吾高科技股份有限公司 | Titanium chloride slag resource utilization method and device |
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| CN100998914A (en) * | 2007-01-11 | 2007-07-18 | 张清 | Treatment method of low grade titanium-riched material chlorination dust collecting slag |
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2013
- 2013-10-12 CN CN201310475987.8A patent/CN103540751A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100998914A (en) * | 2007-01-11 | 2007-07-18 | 张清 | Treatment method of low grade titanium-riched material chlorination dust collecting slag |
Non-Patent Citations (1)
| Title |
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| 余代权: ""四氯化钛生产中废渣的回收利用实践"", 《钛工业进展》, no. 1, 31 December 2002 (2002-12-31), pages 43 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834989A (en) * | 2014-02-24 | 2014-06-04 | 锦州钛业有限公司 | Process of producing calcium sulfate crystal whiskers from chloride-containing wastewater generated in chloride process titanium dioxide production |
| CN105107830A (en) * | 2015-09-24 | 2015-12-02 | 云南新立有色金属有限公司 | Method for treating boiling chlorination waste residue |
| CN105107830B (en) * | 2015-09-24 | 2017-12-08 | 云南冶金新立钛业有限公司 | Method for treating boiling chlorination waste residue |
| CN108372185A (en) * | 2018-04-20 | 2018-08-07 | 江苏久吾高科技股份有限公司 | A kind of titanium chloride slag resource utilization method and its device |
| CN108372185B (en) * | 2018-04-20 | 2024-05-03 | 江苏久吾高科技股份有限公司 | Titanium chloride slag resource utilization method and device |
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Application publication date: 20140129 |