CN101948147A - Processing method of vanadium-precipitation wastewater in vanadium oxide production - Google Patents
Processing method of vanadium-precipitation wastewater in vanadium oxide production Download PDFInfo
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- CN101948147A CN101948147A CN2010102902384A CN201010290238A CN101948147A CN 101948147 A CN101948147 A CN 101948147A CN 2010102902384 A CN2010102902384 A CN 2010102902384A CN 201010290238 A CN201010290238 A CN 201010290238A CN 101948147 A CN101948147 A CN 101948147A
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- vanadium
- material piece
- waste residue
- vanadium oxide
- wastewater
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention provides a processing method of vanadium-precipitation wastewater in vanadium oxide production, comprising the following steps: carrying out evaporation and concentrated crystallization on the vanadium-precipitation wastewater in the vanadium oxide production; manufacturing waste residues obtained after the evaporation and concentrated crystallization into material blocks with holes; and roasting the material blocks. According to the processing method of the vanadium-precipitation wastewater in the vanadium oxide production, the waste residues can be more fully roasted and ammonium sulfate can be more thoroughly decomposed because of manufacturing the waste residues obtained after the evaporation and concentration into the material blocks with the holes and then roasting.
Description
Technical field
The present invention relates to a kind of treatment process of producing the vanadium wastewater of vanadium oxide, more particularly, relate to a kind of method of utilizing the waste residue after calcination process precipitation waste water concentrates.
Background technology
The technical process of traditional production Vanadium Pentoxide in FLAKES mainly contains raw materials pretreatment (comprising vanadium slag fragmentation, pulverizing, batching, batch mixing), oxidizing roasting, grog leaching, precipitation and melts five operations.Wherein, in precipitation technology,, adopt the ammonium salt precipitator method usually in order to produce high-grade Vanadium Pentoxide in FLAKES.Adopt the ammonium salt precipitator method to carry out the trade effluent that the precipitation meeting produces compositions such as a large amount of contains sodium sulfate, ammonium sulfate.
The method of handling vanadium wastewater has multiple, and wherein a kind of method is that the waste residue that obtains after vanadium wastewater is concentrated carries out roasting, makes ammonium sulfate be decomposed into sulfurous gas and ammonia and removes from waste residue, thereby recycle remaining waste residue.When adopting this method, sodium sulfate in the waste residue and ammonium sulfate easily generate low melting point at roasting process, make that waste residue is difficult for grilling thoroughly, and ammonium sulfate decomposes not exclusively, and the thickness requirement of the roasting bed of material is very thin.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, and a kind of waste residue roasting after vanadium wastewater is concentrated method completely is provided.
Treatment process according to the vanadium wastewater of production vanadium oxide of the present invention may further comprise the steps: evaporating, concentrating and crystallizing is produced the vanadium wastewater of vanadium oxide; The waste residue that obtains behind the condensing crystal is made tool foraminous material piece; The roasting material piece.
In an embodiment of the present invention, the waste residue at any place arrives the shortest distance on hole or material piece surface less than 20mm in the material piece.
The shape in hole can be circle.When the hole be shaped as circle the time, the diameter in hole is greater than 10mm.
The shape in hole can be rectangle.When the hole be shaped as rectangle the time, the length and width of rectangular opening are all greater than 10mm.
In another embodiment of the present invention, the material piece can be square, rectangular parallelepiped or right cylinder.
Maturing temperature can be 450 ℃ to 850 ℃.
Therefore, can make the waste residue roasting after vanadium wastewater concentrates complete according to the treatment process of the vanadium wastewater of production vanadium oxide of the present invention, thereby improve the roasting thickness of the waste residue in the stove, utilize stove fully.
Description of drawings
Fig. 1 is the synoptic diagram according to the waste residue material piece of first embodiment of the invention;
Fig. 2 is the synoptic diagram according to the waste residue material piece of second embodiment of the invention;
Fig. 3 is the synoptic diagram according to the waste residue material piece of third embodiment of the invention;
Fig. 4 is the synoptic diagram according to the waste residue material piece of fourth embodiment of the invention.
Embodiment
Below, will describe in detail according to embodiments of the invention in conjunction with the accompanying drawings.
The main component of the crystallisate after the vanadium oxide factory effluent evaporation concentration is sodium sulfate and ammonium sulfate, and particularly, crystallisate can comprise the ammonium sulfate of 50-80% sodium sulfate and 10-40%, in addition, can also have a spot of free-water and crystal water.In this application, unless stated otherwise, otherwise per-cent is all represented weight percent.
In order effectively the sodium sulfate in the crystallisate to be separated with ammonium sulfate, the present invention's employing will be produced the waste residue that obtains after the vanadium wastewater evaporation concentration of vanadium oxide and be made the method that tool foraminous material piece carries out roasting then, ammonium salt is decomposed, thereby obtain the higher sodium sulfate of purity.
The reaction principle of ammonium sulfate roasting reaction is: 3 (NH
4)
2SO
4→ 3SO
2↑+6H
2O+N
2↑+4NH
3↑.With reference to this reaction principle as can be known, ammonium sulfate is decomposed into sulfurous gas, water vapour, nitrogen and ammonia in high-temperature calcination process; And sodium sulfate is stable under hot conditions decomposition reaction does not take place, thereby after roasting finished, the main component of the crystallisate after the vanadium oxide factory effluent evaporation concentration was a sodium sulfate.
In above-mentioned steps, the waste residue that obtains behind the vanadium wastewater condensing crystal is made tool foraminous material piece, carry out roasting then, like this, the hot gas that produces during baking heat can enter in the hole of material piece, heating material piece in the hole, thereby increase heating-surface area, make the material piece obtain effective roasting waste residue.Simultaneously, the flue gas that produces in the roasting process also can in time overflow from the hole of material piece, accelerates roasting speed.
In aforesaid method, can make in the material piece waste residue at any place to the hole or the shortest distance on material piece surface less than 20mm, can guarantee that like this waste residue of expecting everywhere in the piece can grill thoroughly in roasting process, it is complete that ammonium sulfate is decomposed.If the shortest distance that the waste residue at any place arrives hole or material piece surface in the material piece then can make waste residue be difficult to grill thoroughly because of the waste residue layer is too thick, and the flue gas that ammonium sulfate decomposites can't successfully overflow greater than 20mm.
In addition, the hole in the material piece can be circle, also can be rectangle.When the hole in the material piece was circle, the diameter in hole was greater than 10mm; When the hole in the material piece was rectangle, the length and width of rectangular opening were all greater than 10mm.Like this, has the turnover of enough space heat supply gas in the hole of material piece and the overflowing of the flue gas that decomposes.What therefore, the roasting of material piece was carried out is more abundant, more thorough and more complete.Yet the hole of material piece of the present invention is not limited to above-mentioned circle and rectangle, and the hole of material piece can be shape arbitrarily, as long as the hole that forms can make roasting hot gas circulate fully.
The above-mentioned waste residue finish mix piece that obtains after being concentrated by vanadium wastewater can be cubes, rectangular parallelepiped and right cylinder, but the present invention is not limited to this.
In the step of above-mentioned roasting, adopt 450 ℃ to 850 ℃ maturing temperature by waste residue finish mix piece.To carrying out roasting by waste residue finish mix piece, the ammonium sulfate in the material piece decomposes fully under this temperature, and can too high the making of Yin Wendu not expect that sodium sulfate generation fusion makes roasting apparatus impaired in the piece.
In above-mentioned steps, the waste residue that can utilize the molding device of brick press, pressing machine, honey-comb briquet etc. for example that the vanadium wastewater evaporating, concentrating and crystallizing is obtained is shaped to shapes such as perforated brick, hollow brick, honeycomb briquette, and the material bulk strength after the moulding does not need too big, does not collapse in roasting process as long as guarantee the material piece.
According to above-mentioned step the waste water of producing vanadium oxide is handled, ammonium sulfate decomposes generation sulfurous gas and ammonia after the roasting, enters in the flue gas, thereby removes from waste residue.Entering sulfur in smoke and ammonia can reclaim respectively, thereby is used.The quality percentage composition of the sodium sulfate in the waste residue that obtains after the roasting can be used as product and sells greater than 95%.
Embodiment 1
Fig. 1 is the synoptic diagram according to the waste residue material piece of first embodiment of the invention.At first, be that (main component is NH to waste residue with the vanadium wastewater evaporating, concentrating and crystallizing of producing vanadium oxide
4 +5.36%, Na
+19.10%, moisture 20.35%).Then, utilize block machine will produce the rectangular parallelepiped material piece that the waste residue that obtains behind the vanadium wastewater evaporative crystallization of vanadium oxide is made 230mm * 120mm * 90mm.With reference to Fig. 1, be formed with the circular port that a plurality of diameters are 20mm, the ultimate range d between the adjacent holes in the material piece of rectangular parallelepiped
1Be 29.5mm, the shortest distance d between the adjacent holes
2Be 20mm, the hole to side surface apart from d
3Be 15mm.At last, should expect that piece put into stove and carry out roasting.The temperature of stove clinkering zone is 650 ℃, is 1 hour in the clinkering zone residence time.The purity of the sodium sulfate product in the waste residue that obtains after the roasting is 96.12%, NH
4 +Content＜0.1%.
Embodiment 2
Fig. 2 is the synoptic diagram according to the waste residue material piece of second embodiment of the invention.At first, be that (main component is NH to waste residue with the vanadium wastewater evaporating, concentrating and crystallizing of producing vanadium oxide
4 +5.36%, Na
+19.10%, moisture 20.35%).Then, the waste residue that utilizes honey-comb briquet to produce to obtain behind the vanadium wastewater evaporative crystallization of vanadium oxide is finish mix.With reference to Fig. 2, the right cylinder of the honeycomb coaly that this material piece is diameter 200mm, high 100mm wherein, is formed with the circular port that a plurality of diameters are 20mm, the ultimate range d between the adjacent holes in the material piece
1Be 33.64mm, the shortest distance d between the adjacent holes
2Be 15mm, the hole to side surface apart from d
3Be 15mm.At last, should expect that piece put into stove and carry out roasting.The temperature of stove clinkering zone is 450 ℃, is 2 hours in the clinkering zone residence time.The purity of sodium sulfate product is 96.59% in the waste residue that obtains after the roasting, NH
4 +Content＜0.1%.
Fig. 3 is the synoptic diagram according to the waste residue material piece of third embodiment of the invention.At first, be that (main component is NH to waste residue with the vanadium wastewater evaporating, concentrating and crystallizing of producing vanadium oxide
4 +5.36%, Na
+19.10%, moisture 20.35%).Then, utilizing block machine will produce the waste residue that obtains behind the vanadium wastewater evaporative crystallization of vanadium oxide makes 240mm * 115mm * 90mm and expects piece.With reference to Fig. 3, this material piece is the rectangular parallelepiped of hollow brick shape, wherein, is formed with the slot of two long 90mm, wide 75mm in the material piece, and the thickness of each wall of this material piece is 20mm, that is, and and d
1=d
2=d
3=20mm.At last, will expect that piece puts into stove and carry out roasting.The temperature of stove clinkering zone is 850 ℃, is 0.5 hour in the clinkering zone residence time.The purity of the sodium sulfate product in the waste residue that obtains after the roasting is 97.03%, NH
4 +Content＜0.1%.
Embodiment 4
Fig. 4 is the synoptic diagram according to the waste residue material piece of fourth embodiment of the invention.At first, be that (main component is NH to waste residue with the vanadium wastewater evaporating, concentrating and crystallizing of producing vanadium oxide
4 +5.36%, Na
+19.10%, moisture 20.35%).Then, utilizing block machine will produce the waste residue that obtains behind the vanadium wastewater evaporative crystallization of vanadium oxide makes 240mm * 115mm * 90mm and expects piece.With reference to Fig. 4, this material piece is the slot with a plurality of long 35mm, wide 27.5mm, and the thickness of each wall of the material piece of this rectangular build is 20mm, that is, and and d
1=d
2=d
3=20mm.At last, should expect that piece put into stove and carry out roasting.The temperature of stove clinkering zone is 650 ℃, is 1 hour in the clinkering zone residence time.The purity of the sodium sulfate product in the waste residue that obtains after the roasting is 96.82%, NH
4 +Content＜0.1%.
The comparative example
At first, be that (main component is NH to waste residue with the vanadium wastewater evaporating, concentrating and crystallizing of producing vanadium oxide
4 +5.36%, Na
+19.10%, moisture 20.35%).Then, utilize block machine will produce the waste residue that obtains behind the vanadium wastewater evaporative crystallization of vanadium oxide and make the solid material piece of 240mm * 115mm * 90mm.Should expect that piece put into stove and carry out roasting.The temperature of stove clinkering zone was 650 ℃, 1 hour clinkering zone residence time.Material piece surface forms the shell of one deck white after the roasting, and the waste residue of material piece inside is a grey, and by assay, the content of the sodium sulfate after the roasting in the material piece is 85.46%, NH
4 +Be 2.07%.
From each top embodiment 1 to 4 and comparative example's description as can be seen, make the method that tool foraminous material piece carries out roasting then according to the waste residue behind the vanadium wastewater evaporating, concentrating and crystallizing that will produce vanadium oxide of the embodiment of the invention, make that waste residue is easier to be grilled thoroughly, ammonium sulfate decomposes fully.
Claims (8)
1. treatment process of producing the vanadium wastewater of vanadium oxide, this method may further comprise the steps:
Evaporating, concentrating and crystallizing is produced the vanadium wastewater of vanadium oxide;
The waste residue that obtains behind the condensing crystal is made tool foraminous material piece;
The roasting material piece.
2. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 1 is characterized in that, the waste residue at any place arrives the shortest distance on hole or material piece surface less than 20mm in the material piece.
3. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 2 is characterized in that, the hole be shaped as circle.
4. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 3 is characterized in that, the diameter in hole is greater than 10mm.
5. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 2 is characterized in that, the hole be shaped as rectangle.
6. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 5 is characterized in that, the length and width of rectangular opening are all greater than 10mm.
7. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 1 is characterized in that, the material piece is square, rectangular parallelepiped or right cylinder.
8. the treatment process of the vanadium wastewater of production vanadium oxide as claimed in claim 1 is characterized in that, maturing temperature is 450 ℃ to 850 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102902384A CN101948147B (en) | 2010-09-25 | 2010-09-25 | Processing method of vanadium-precipitation wastewater in vanadium oxide production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102902384A CN101948147B (en) | 2010-09-25 | 2010-09-25 | Processing method of vanadium-precipitation wastewater in vanadium oxide production |
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| Publication Number | Publication Date |
|---|---|
| CN101948147A true CN101948147A (en) | 2011-01-19 |
| CN101948147B CN101948147B (en) | 2012-02-08 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704303A (en) * | 2020-07-09 | 2020-09-25 | 攀枝花学院 | Drying method of evaporation crystallization liquid of vanadium precipitation wastewater and method for recycling sodium sulfide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999354A (en) * | 2006-11-07 | 2007-07-18 | 刘强国 | Treatment of waste water in vanadium pentaoxide production and its full circulation technology |
| CN101358282A (en) * | 2008-08-26 | 2009-02-04 | 攀钢集团研究院有限公司 | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water |
| CN101712491A (en) * | 2009-09-28 | 2010-05-26 | 雷在荣 | Process method for producing vanadic oxide from vanadium-contained wastewater slag |
| CN101812593A (en) * | 2010-04-22 | 2010-08-25 | 攀钢集团钢铁钒钛股份有限公司 | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt |
-
2010
- 2010-09-25 CN CN2010102902384A patent/CN101948147B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999354A (en) * | 2006-11-07 | 2007-07-18 | 刘强国 | Treatment of waste water in vanadium pentaoxide production and its full circulation technology |
| CN101358282A (en) * | 2008-08-26 | 2009-02-04 | 攀钢集团研究院有限公司 | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water |
| CN101712491A (en) * | 2009-09-28 | 2010-05-26 | 雷在荣 | Process method for producing vanadic oxide from vanadium-contained wastewater slag |
| CN101812593A (en) * | 2010-04-22 | 2010-08-25 | 攀钢集团钢铁钒钛股份有限公司 | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111704303A (en) * | 2020-07-09 | 2020-09-25 | 攀枝花学院 | Drying method of evaporation crystallization liquid of vanadium precipitation wastewater and method for recycling sodium sulfide |
| CN111704303B (en) * | 2020-07-09 | 2022-06-21 | 攀枝花学院 | Drying method of evaporation crystallization liquid of vanadium precipitation wastewater and method for recycling sodium sulfide |
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| CN101948147B (en) | 2012-02-08 |
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