CN1724406A - Process for treating industrial waste water containing chromium, vanadium - Google Patents
Process for treating industrial waste water containing chromium, vanadium Download PDFInfo
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- CN1724406A CN1724406A CN 200510017724 CN200510017724A CN1724406A CN 1724406 A CN1724406 A CN 1724406A CN 200510017724 CN200510017724 CN 200510017724 CN 200510017724 A CN200510017724 A CN 200510017724A CN 1724406 A CN1724406 A CN 1724406A
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- chromium
- vanadium
- industrial wastewater
- sodium metabisulfite
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Abstract
A process for treating the industrial sewage containing Cr and V includes such steps as preparing the solution of sodium pyro-sulfite, proportionally adding it to the sewage in reduction tank, reducing the 6-valence Cr to 3-valence Cr, proportionally adding the solution of sodium hydroxide to the sewage in neutralizing tank for reaction between V2O2 and sodium hydroxide to generate Na2V4O9 * 4H2O, reaction between V4O9 and said 3-valence Cr to generate Cr2(V4O9)3 deposit and changing residual 3-valence Cr to chromium hydroxide deposit, regulating pH=7.5-8.5, clarifying, and press filtering of suspended substance.
Description
Technical Field
The invention relates to a method for treating industrial wastewater, in particular to a method for treating industrial wastewater containing chromium and vanadium.
Background
At present, industrial wastewater generated during the production of vanadium trioxide and vanadium pentoxide often contains a large amount of chromium and vanadium, wherein the total chromium content is about 1g/L, the vanadium content is about 0.1g/L, and hexavalent chromium is extremely toxic, and the strict treatment requirements are clearly established in ChinaThe discharge of chromium-containing industrial wastewater is regulated, the toxicity of vanadium compounds is high, and the environment is seriously polluted by overhigh vanadium content in the industrial wastewater, thereby causing serious threat to the health of people. The industrial wastewater is acidic, and contains ions mainly including H+，Cr3+，Cr6+，NH4 +，SO4 2-，VO3 -The ion to be treated is Cr3+，Cr6+，VO3 -Wherein, in an acidic environment, the ions in the solution exist in the following forms:
because the ratio of chromium to vanadium in the wastewater, the balance of the above list shifts to the right, vanadium exists mainly in a tetravalent state and combines with sulfate radicals in the wastewater to form V2O2(SO4)。
At present, the method for treating the wastewater usually adopts an electrolytic method, an ion exchange method, an adsorptionmethod, a reverse osmosis method and a chemical reduction method, the most common method is a process of adding ferrous sulfate to reduce 6-valent chromium and adding lime to neutralize acid, although the discharged water treated by the methods can reach the relevant national discharge standard, the treatment cost is higher, the process is complex, the treatment effect is poor, the amount of generated waste residues is large, the filter pressing equipment is in overload operation, and in addition, the ideal treatment result of vanadium and chromium cannot be obtained.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides the method for treating the industrial wastewater containing chromium and vanadium, which has the advantages of simple process, good treatment effect and low investment cost.
The technical scheme for treating the industrial wastewater containing chromium and vanadium provided by the invention is as follows: (1) preparing a sodium metabisulfite solution for later use, wherein the concentration of the sodium metabisulfite solution is 28-54%, and the pH value of the sodium metabisulfite solution is 3.6-5.7; (2) putting the industrial wastewater containing chromium and vanadium into a reduction tank, and adding the sodium metabisulfite solution in a metering manner to reduce hexavalent chromium in the industrial wastewater containing chromium and vanadium into trivalent chromium; (3) and then handle(2) Putting the wastewater into a neutralization tank, and adding a sodium hydroxide solution in a metering manner to ensure that V in the industrial wastewater containing chromium and vanadium2O2 4+Reacting with sodium hydroxide to generate Na2V4O9·4H2O, wherein V4O9 2-And reacts with trivalent chromium to form Cr2(V4O9)3Precipitating, completely forming chromium hydroxide precipitate by the rest trivalent chromium, and finally adjusting the pH value to 7.5-8.5; (4) and (3) placing the wastewater in the clarification tank for clarification and separation, sending suspended matters to a filter press for filter pressing and then carrying out centralized treatment, and carrying out additional treatment on supernatant and filtrate.
In the treatment method, the acidic sodium metabisulfite solution is utilized to fully reduce hexavalent chromium in the wastewater into trivalent chromium, and sodium hydroxide is added to ensure that V is converted into2O2 4+Reaction to form Na2V4O9·4H2O, and skillfully make V4O9 2-And combined with trivalent chromium to form Cr2(V4O9)3Precipitating, and completely forming chromium hydroxide precipitate by the rest trivalent chromium; the method not only fully reduces the highly toxic hexavalent chromium contained in the industrial wastewater, but also ingeniously leads the vanadium in the industrial wastewater to react with the trivalent chromium to form Cr2(V4O9)3The precipitation well solves the problem of environmental pollution caused by vanadium, and simultaneously, trivalent chromium is fully precipitated, so that the total chromium content in the industrial wastewater is greatly reduced.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
In order to better illustrate the technical solution of the present invention and the advantages thereof, two specific embodiments are given:
example 1: the method for treating the industrial wastewater containing chromium and vanadium comprises the following steps: (1) preparing a sodium metabisulfite solution for later use, wherein the concentration of the sodium metabisulfite solution is 38-42%, and the pH value of the sodium metabisulfite solution is 4.2; (2) putting the industrial wastewater containing chromium and vanadium into a reduction tank according to Cr6+With Na2S2O5The molar ratio is 4: 3-3.5, the sodium metabisulfite solution is added in a metered manner, so that hexavalent chromium in the chromium and vanadium-containing industrial wastewater is reduced into trivalent chromium; (3) putting the wastewater of the step (2) into a neutralization tank, and adding a sodium hydroxide solution in a metering manner to ensure that V in the industrial wastewater containing chromium and vanadium2O2 4+Reacting with sodium hydroxide to generate Na2V4O9·4H2O, wherein V4O9 2-And reacts with trivalent chromium to form Cr2(V4O9)3Precipitating, completely forming chromium hydroxide precipitate by the rest trivalent chromium, and finally adjusting the pH value to 7.8-8.1, wherein under the condition, the chromium hydroxide and the Cr are2(V4O9)3The two precipitates are adsorbed together to form coprecipitation; (4) and (3) placing the wastewater in the clarification tank for clarification and separation, sending suspended matters to a filter press for filter pressing and then carrying out centralized treatment, and carrying out additional treatment on supernatant and filtrate.
Example2: the method for treating the industrial wastewater containing chromium and vanadium comprises the following steps: (1) preparing a sodium metabisulfite solution for later use, wherein the concentration of the sodium metabisulfite solution is 40-42%, and the pH value of the sodium metabisulfite solution is 4.5; (2) putting the industrial wastewater containing chromium and vanadium into a reduction tank according to Cr6+With Na2S2O5The sodium metabisulfite solution is metered and added according to the molar ratio of 4: 3.2-3.4, so that hexavalent chromium in the chromium-vanadium-containing industrial wastewater is reduced into trivalent chromium; (3) putting the wastewater of the step (2) into a neutralization tank, and adding a sodium hydroxide solution in a metering manner to ensure that V in the industrial wastewater containing chromium and vanadium2O2 4+Reacting with sodium hydroxide to generate Na2V4O9·4H2O, wherein V4O9 2-And reacts with trivalent chromium to form Cr2(V4O9)3Precipitating, completely forming chromium hydroxide precipitate by the rest trivalent chromium, and finally adjusting the pH value to 8.0-8.1, wherein under the condition, the chromium hydroxide and the Cr are2(V4O9)3The two precipitates are adsorbed together to form coprecipitation; (4) and (3) placing the wastewater in the clarification tank for clarification and separation, sending suspended matters to a filter press for filter pressing and then carrying out centralized treatment, and carrying out additional treatment on supernatant and filtrate.
The following are several comparative tests of the treatment method of industrial wastewater containing chromium and vanadium adopted by the invention and the prior art:
table (one):
| ferrous sulfate lime process | The process | ||||
| Total chromium | Before treatment | After treatment | Before treatment | After treatment | |
| 1.10g/L | 0.05g/L | 1.10g/L | 0.003g/L | ||
| Total vanadium | 0.11g/L | ＜0.01g/L | 0.11g/L | ＜0.001g/L | |
| The added amount of ferrous sulfate is Kg/ton of water | 13.0 | Sodium metabisulfite adding amount Kg/ton water | 2.3 | ||
| Medicine price bit/ton per ton of waste water | 9.36 | Medicine price bit/ton per ton of waste water | 5.52 | ||
| Production slag weight Kg/ton water | 38 | Production slag weight Kg/ton water | 3.4 | ||
Table (ii):
| ferrous sulfate lime process | The process | ||||
| Total chromium | Before treatment | After treatment | Before treatment | After treatment | |
| 1.13g/L | 0.05g/L | 1.13g/L | 0.003g/L | ||
| Total vanadium | 0.12g/L | ＜0.05g/L | 0.12g/L | ＜0.001g/L | |
| The added amount of ferrous sulfate is Kg/ton of water | 13.5 | Sodium metabisulfite adding amount Kg/ton water | 2.5 | ||
| Medicine price bit/ton per ton of waste water | 9.72 | Medicine price bit/ton per ton of waste water | 6.0 | ||
| Production slag weight Kg/ton water | 38.4 | Production slag weight Kg/ton water | 3.6 | ||
Table (iii):
| ferrous sulfate lime process | The process | ||||
| Total chromium | Before treatment | After treatment | Before treatment | After treatment | |
| 1.15g/L | 0.05g/L | 1.15g/L | 0.003g/L | ||
| Total vanadium | 0.13g/L | ＜0.05g/L | 0.13g/L | ＜0.001g/L | |
| The added amount of ferrous sulfate is Kg/ton of water | 14.0 | Sodium metabisulfite adding amount Kg/ton water | 2.7 | ||
| Medicine price bit/ton per ton of waste water | 10.08 | Medicine price bit/ton per ton of waste water | 6.48 | ||
| Production slag weight Kg/ton water | 38.8 | Production slag weight Kg/ton water | 3.8 | ||
Table (iv):
| ferrous sulfate lime process | The process | ||||
| Total chromium | Before treatment | After treatment | Before treatment | After treatment | |
| 1.09g/L | 0.05g/L | 1.09g/L | 0.003g/L | ||
| Total vanadium | 0.10g/L | ＜0.05g/L | 0.10g/L | ＜0.001g/L | |
| The added amount of ferrous sulfate is Kg/ton of water | 12.5 | Sodium metabisulfite adding amount Kg/ton water | 2.1 | ||
| Medicine price bit/ton per ton of waste water | 9.0 | Medicine price bit/ton per ton of waste water | 5.02 | ||
| Production slag weight Kg/ton water | 37.9 | Production slag weight Kg/ton water | 3.2 | ||
The following can be seen from table (a), table (b), table (c) and table (d):
① compared with the existing technology, the technology for processing the industrial wastewater containing chromium and vanadium has lower chromium and vanadium content, little pollution to the environment, and is more suitable for the wastewater discharge standard;
② for the production cost, comparing the use of ferrous sulfate and sodium metabisulfite, the cost of each ton of waste water can be reduced by 3.5-4.0 yuan.
③ the slag discharge amount of the process is far less than that of the existing process, the processing capacity of the existing filtering equipment can completely adapt to the processing requirement of the process, and the labor intensity of workers and various consumptions of the equipment can be reduced.
Claims (1)
1. A method for treating industrial wastewater containing chromium and vanadium is characterized by comprising the following steps: (1) preparing a sodium metabisulfite solution for later use, wherein the concentration of the sodium metabisulfite solution is 28-54%, and the pH value of the sodium metabisulfite solution is 3.6-5.7; (2) putting the industrial wastewater containing chromium and vanadium into a reduction tank, and adding the sodium metabisulfite solution in a metering manner to reduce hexavalent chromium in the industrial wastewater containing chromium and vanadium into trivalent chromium; (3) putting the wastewater of the step (2) into a neutralization tank, and adding a sodium hydroxide solution in a metering manner to ensure that V in the industrial wastewater containing chromium and vanadium2O2 4+Reacting with sodium hydroxide to generate Na2V4O9·4H2O, wherein V4O9 2-And reacts with trivalent chromium to form Cr2(V4O9)3Precipitating, completely forming chromium hydroxide precipitate by the rest trivalent chromium, and finally adjusting the pH value to 7.5-8.5; (4) and (3) placing the wastewater in the clarification tank for clarification and separation, sending suspended matters to a filter press for filter pressing and then carrying out centralized treatment, and carrying out additional treatment on supernatant and filtrate.
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| CNB2005100177248A CN100400435C (en) | 2005-06-20 | 2005-06-20 | Process for treating industrial waste water containing chromium, vanadium |
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| CNB2005100177248A CN100400435C (en) | 2005-06-20 | 2005-06-20 | Process for treating industrial waste water containing chromium, vanadium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497675C (en) * | 2006-08-10 | 2009-06-10 | 中国科学院过程工程研究所 | Method for separating and reclaiming vanadium and chromium from solution containing vanadium and chromium |
| CN101830591A (en) * | 2010-04-15 | 2010-09-15 | 竹山中强钒业制造有限公司 | Water recycling method for use in extraction process of vanadium pentoxide |
| CN102476887A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of vanadium recovery wastewater |
| CN102627372A (en) * | 2012-04-19 | 2012-08-08 | 波鹰(厦门)科技有限公司 | Method for treating vanadium pentoxide wastewater and circularly utilizing resources |
| CN102876895A (en) * | 2012-10-09 | 2013-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium and chromium from low-concentration pentavalent vanadium and hexavalent chromium mixed liquor |
| CN106186064A (en) * | 2016-07-26 | 2016-12-07 | 大连博融新材料股份有限公司 | A kind of method that degree of depth produces high-purity ammonium metavanadate except chromium |
| CN108640383A (en) * | 2018-04-14 | 2018-10-12 | 中信锦州金属股份有限公司 | A kind of technique and its system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation |
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| CN101979341B (en) * | 2010-10-12 | 2011-11-30 | 重庆大学 | Vanadium and chromium heavy metal ions-containing leaching ore waste water treatment method |
Family Cites Families (3)
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| US6270679B1 (en) * | 1995-05-19 | 2001-08-07 | Lawrence Kreisler | Method for recovering and separating metals from waste streams |
| CN1371875A (en) * | 2001-02-28 | 2002-10-02 | 上海理日科技发展有限公司 | Complete set waste water treatment technology and automatic controller thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100497675C (en) * | 2006-08-10 | 2009-06-10 | 中国科学院过程工程研究所 | Method for separating and reclaiming vanadium and chromium from solution containing vanadium and chromium |
| CN101830591A (en) * | 2010-04-15 | 2010-09-15 | 竹山中强钒业制造有限公司 | Water recycling method for use in extraction process of vanadium pentoxide |
| CN102476887A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of vanadium recovery wastewater |
| CN102627372A (en) * | 2012-04-19 | 2012-08-08 | 波鹰(厦门)科技有限公司 | Method for treating vanadium pentoxide wastewater and circularly utilizing resources |
| CN102627372B (en) * | 2012-04-19 | 2013-06-12 | 波鹰(厦门)科技有限公司 | Method for treating vanadium pentoxide wastewater and circularly utilizing resources |
| CN102876895A (en) * | 2012-10-09 | 2013-01-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium and chromium from low-concentration pentavalent vanadium and hexavalent chromium mixed liquor |
| CN106186064A (en) * | 2016-07-26 | 2016-12-07 | 大连博融新材料股份有限公司 | A kind of method that degree of depth produces high-purity ammonium metavanadate except chromium |
| CN108640383A (en) * | 2018-04-14 | 2018-10-12 | 中信锦州金属股份有限公司 | A kind of technique and its system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation |
| CN108640383B (en) * | 2018-04-14 | 2021-07-06 | 中信锦州金属股份有限公司 | Process and system for improving operation period of vanadium pentoxide stripping deamination tower |
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| CN100400435C (en) | 2008-07-09 |
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