CN1603249A - Heavy metal precipitating agent - Google Patents
Heavy metal precipitating agent Download PDFInfo
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- CN1603249A CN1603249A CN 200410051386 CN200410051386A CN1603249A CN 1603249 A CN1603249 A CN 1603249A CN 200410051386 CN200410051386 CN 200410051386 CN 200410051386 A CN200410051386 A CN 200410051386A CN 1603249 A CN1603249 A CN 1603249A
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- heavy metal
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- precipitator
- metal ion
- precipitation
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Abstract
The invention discloses a heavy metal precipitator. It conquers the disadvantages of low utilization factor of raw material, and weak complexation ability, incompact wadding and slow speed to deposit existed in the heavy metal precipitator in existing.Especially for the stability complexation heavy metal ion wasting water, it can remove stability heavy metal ion. Moreover, it has decolor function and can be used in the process for heavy metal ion.
Description
Technical field
The present invention relates to a kind of precipitation agent, especially a kind of heavy metal precipitator.
Background technology
Heavy metal is meant that proportion greater than 4 or 5 metal, has 45 kinds, approximately as copper, lead, zinc, iron, cobalt, nickel, vanadium, niobium, tantalum, titanium, manganese, cadmium, mercury, tungsten, molybdenum, gold and silver etc.The pollution of these metals is long-standing worldwide environmental problems, in the U.S. 20000-50000 mouth depleted mine is just arranged according to statistics, the annual waste water (the following heavy metal ion that will contain is called for short heavy metal wastewater thereby) that contains heavy metal ion in a large number that produces of these mines, they affect the water quality in 23000 kilometers rivers of the U.S.; The quantity discharged of annual whole world mercury is above 3000 tons.Along with the develop rapidly of modern industry, the quantity discharged of heavy metal industrial effluent increases day by day.The industry of discharging heavy metal wastewater thereby also has closely-related circuit board plant of IT industry and microelectronics industry with present Fang Xinwei Chinese mugwort except traditional mining, Sweet natural gas, papermaking, plating, medal polish and chlorine industry.The concentration that has been found that the heavy metal ions in wastewater that the municipal sewage plant excludes at present has trend of rising day by day.Therefore, many countries have all taked strict legislation to avoid the pollution of heavy metal with the protection face of land and underground water.In order to satisfy strict environmental protection needs, everyway is paid attention to the control of heavy metal contamination especially.Though the effort through experts and scholars and technician is opened up, but still find the method for perfect removal heavy metal.
Handle the heavy metal wastewater thereby common method chemical precipitation method, absorption method, membrane filtration and ion exchange method etc. are arranged.Although above-mentioned four kinds of methods have their own characteristics each, by contrast, chemical precipitation method is still all having tangible competitive edge in cost of investment aspect the working cost.The most common with precipitation of hydroxide and sulfide precipitation in chemical precipitation method, but these two kinds of methods all have its limitation.The one, acid is dissolved again or oxidation by air is decomposed but the precipitation that these two kinds of methods produce all can be met, produce secondary public hazards etc., the 2nd, sludge moisture content is big, precipitation not exclusively, therefore this method is difficult to make the complete qualified discharge of many heavy metal wastewater therebies, particularly for the waste water that contains stable comple, this method is powerless especially.Therefore, the processing of complexing heavy metal wastewater thereby is to pollute one of the focus in Control Study field and difficult point problem always.In view of the foregoing, many in the world major companies have begun one's study and development of new heavy metal containing wastewater treatment medicament over past ten years.
One of product of selling on the world market is TiO-Red at present, and it is that ETUS company developed in 1994.The said firm claims that TiO-Red removes heavy metal by thiocarbonate, but people's such as nearest Henke result of study shows that TiO-Red is actually thiocarbonate, a kind of mixture of sulfide and other compound, it finally is by sulfide precipitation place to go heavy metal ion.
U.S. Degussa company had developed another kind of heavy metal precipitator TMT-55 in 1993.The main component of this product is a trithio triazine acid sodium.Although it is very few that relevant this product is removed the mechanism report of heavy metal ion, from the molecular structure of trithio triazine acid sodium, it does not have enough reaction site and heavy metal ion to form coordinate bond and can only form ionic linkage.Degussa company admits that also the solubility product of TMT-metal is bigger but only similar with metallic sulfide than oxyhydroxide, and its pH use range is narrow, can not form long-time stable precipitated metal thing, surpasses the stripping that will observe metal ion in 78 days.
The heavy metal precipitator of selling on the world market also has HMP-2000 at present, and it is that Adderson company developed in 1999.Its main component is a thiocarbamate, have every year 1.5 hundred ten thousand tons of heavy metal wastewater thereby waste water to handle with HMP-2000 in the U.S. at present, but it is lower to the processing efficiency of complexing heavy metal wastewater thereby.
Summary of the invention
The object of the present invention is to provide and a kind ofly overcome that the raw material availability that existing heavy metal precipitator exists is not high, complex ability is strong, flco is loose and sedimentation speed waits slowly, the shortcoming of particularly not having special effect agent at stable complexation heavy metal ion waste water provides a kind of and removes effectively and the fixing heavy metal precipitator of heavy metal ion.
Another object of the present invention is to provide a kind of composition heavy metal precipitator.
Another object of the present invention is to provide another kind of composition heavy metal precipitator.
Another object of the present invention is to provide the application of above-mentioned heavy metal precipitator in wastewater treatment.
Heavy metal precipitator of the present invention is N, N-two dithio piperazinecarboxylic acid sodium.
Heavy metal precipitator of the present invention contains 98.5～99 weight %N, N-two dithio piperazinecarboxylic acid sodium and 1～1.5% weight Al
2(SO4)
3Form.
Heavy metal precipitator of the present invention, by 41～93 weight %N, N-two dithio piperazinecarboxylic acid sodium, 5～56 weight % activated carbon powder, 1～1.5 weight %Al
2(SO4)
3Form with 1～1.5 weight %MgSO4.Although existing a few heavy metal precipitator is sold on the world market, these heavy metal precipitators all have certain defective.Consider that from molecular structure we notice that present use and these precipitation agents of being reported all are single basic sequestrants, can only form small molecules inner complex precipitation with metal ion.
Heavy metal precipitator N of the present invention, N-two dithio piperazinecarboxylic acid sodium (BDCP) are a kind of double-basis chelating reagents, the heavy metal ion reaction in energy and the waste water forms stable ligand polymer rapidly.It is than can only more effectively removing heavy metal ion with the precipitation agent that metal ion forms the small molecules inner complex at present.The present invention is applied to the polycoordination chemistry processing of heavy metal wastewater thereby first to improve the deposition efficiency of precipitation agent.Its precipitin reaction is as follows:
Heavy metal precipitator N of the present invention, N-two dithio piperazinecarboxylic acid sodium (BDCP) can also be formed the heavy metal precipitator of new broad-spectrum high efficacy, for example activated carbon powder, Al with other settling agents
2(SO4)
3Or MgSO4 etc., will be among the present invention by 93～41 weight %N, N-two dithio piperazinecarboxylic acid sodium, 5～56 weight % activated carbon powder, 1～1.5 weight %Al
2(SO4)
3The heavy metal precipitator of forming with 1～1.5 weight %MgSO4 is called the CSM heavy metal precipitator.Be use coordination supramolecular chemistry principle prepare a kind of based on the heavy metal precipitator CSM of broad-spectrum high efficacy.Heavy metal ion reaction in this heavy metal precipitator in BDCP energy and the waste water generates stable ligand polymer, and this polymkeric substance forms the macrobead precipitation rapidly under the effect of settling agent.It is not only than can only more effectively removing with the precipitation agent that metal ion forms the small molecules inner complex at present and fixing heavy metal ion, and in the precipitation of heavy metals ion function of can also decolouring simultaneously.The present invention is applied to the polycoordination chemistry processing of heavy metal wastewater thereby first to improve the deposition efficiency of precipitation agent.
The CSM heavy metal precipitator can be prepared by following method:
(1) N, N-two dithio piperazinecarboxylic acid sodium (BDCP) synthetic: 8.6 gram Piperazine anhydrous and 8 gram solid sodium hydroxides added fill in the three-necked bottle of 70～100ml Virahol and 70～100ml ether, then under 5～50 ℃ with 0.5～1mlmin
-1Speed drip 12ml CS
2After 2～8 hours reaction, the suction filtration drying obtains the white solid product, and productive rate is 70～78%.The result of ultimate analysis is C
6H
8N
2S
4Na
2Be N, N-two dithio piperazinecarboxylic acid sodium (BDCP).
(2) with 41～93 weight %BDCP, 5～56 weight % activated carbon powder, 1～1.5 weight %Al
2(SO4)
3Even with 1～1.5 weight %MgSO4 mechanically mixing, promptly obtain the CSM heavy metal precipitator.
When the CSM heavy metal precipitator was used for wastewater treatment, the amount adding CSM by stoichiometric ratio excessive 8～50% stirred 5～20 minutes, carried out solid-liquid separation then.
Heavy metal precipitator of the present invention, the raw material availability that has overcome existing heavy metal precipitator existence is not high, complex ability is strong, flco is loose and sedimentation speed waits slowly, the shortcoming of particularly not having special effect agent at stable complexation heavy metal ion waste water, can remove effectively and fixing heavy metal ion, and, can be applicable to the processing of heavy metal ions in wastewater in the precipitation of heavy metals ion function of can also decolouring simultaneously.
Embodiment
Following embodiment will help those of ordinary skill in the art further to understand the present invention, but not limit the present invention in any form.
Embodiment 1
9.5mg BDCP is added 50ml contain Cu
2+50mg.l
-1CuSO4 waste water in, be 85rmin with rotating speed
-1Agitator stir after 5 minutes, brown precipitate appears in the solution of waste water.After static 4 hours, the turbidity that records solution is 42, remaining Cu in the solution
2+Concentration be 0.6mg.l
-1
Embodiment 2
With 9.5mg BDCP and 0.1mg Al
2(SO
4)
3Add 50ml and contain Cu
2+50mg.l
-1CuSO4 waste water in, be 85rmin with rotating speed
-1Agitator stir after 5 minutes, a large amount of precipitations appear in the waste water.After in static 30 minutes, the turbidity that records solution is 26, remaining Cu in the solution
2+Concentration be 0.1mg.l
-1, they all are lower than the emission standard of national comprehensive wastewater.It is that 6 water was placed Cu 60 days that this precipitation is placed pH
2+Accumulation stripping concentration only be 0.08mg.l
-1
Embodiment 3
With 11mg CSM (45 weight %N, N-two dithio piperazinecarboxylic acid sodium, 53 weight % activated carbon powder, 1.0 weight %Al
2(SO4)
3With 1.0 weight %MgSO4) add 50ml and contain Cu
2+50mg.l
-1CuSO4 waste water in, be 85rmin with rotating speed
-1Agitator stir after 5 minutes, a large amount of precipitations appear in the waste water.After in static 30 minutes, the turbidity that records solution is 16, remaining Cu in the solution
2+Concentration be 0.07mg.l
-1, they all are lower than the emission standard of national comprehensive wastewater.It is that 6 water was placed Cu 60 days that this precipitation is placed pH
2+Accumulation stripping concentration only be 0.079mg.l
-1
Embodiment 4
With 11mg CSM (56 weight %N, N-two dithio piperazinecarboxylic acid sodium, 41.5 weight % activated carbon powder, 1.2 weight %Al
2(SO4)
3With 1.3 weight %MgSO4) add 50ml and contain Cu 50mg.l
-1CuEDTA waste water in, be 85rmin with rotating speed
-1Agitator stir after 5 minutes, a large amount of precipitations appear in the waste water.After in static 30 minutes, the turbidity that records solution is 22, remaining Gu in the solution
2+Concentration be 0.09mg.l
-1, they all are lower than the emission standard of national comprehensive wastewater.It is that 6 water was placed Cu 60 days that this precipitation is placed pH
2+Accumulation stripping concentration only be 0.081mg.l
-1
Embodiment 5
With 11mg CSM (75 weight %N, N-two dithio piperazinecarboxylic acid sodium, 22.5 weight % activated carbon powder, 1.3 weight %Al
2(SO4)
3With 1.2 weight %MgSO4) add 50ml and contain 50mg.l
-1Cu
2+And 100mg.l
-1Be 85rmin with rotating speed in the comprehensive wastewater of reactive brilliant red x-3b
-1Agitator stir after 30 minutes, occur a large amount of precipitations and color in the waste water and effectively removed.After in static 30 minutes, the colourity that records solution is 26, remaining Cu in the solution
2+Concentration be 0.06mg.l
-1, they all are lower than the emission standard of national comprehensive wastewater.
Embodiment 6
With 11mg CSM (90 weight %N, N-two dithio piperazinecarboxylic acid sodium, 7 weight % activated carbon powder, 1.5 weight %Al
2(SO4)
3With 1.5 weight %MgSO4) add 50ml and contain Ni
2+50mg.l
-1The citric acid nickel waste water in, be 85rmin with rotating speed
-1Agitator stir after 5 minutes, a large amount of precipitations appear in the waste water.After in static 30 minutes, the turbidity that records solution is 23, remaining Ni in the solution
2+Concentration be 0.08mg.l
-1, they all are lower than the emission standard of national comprehensive wastewater.It is that 6 water was placed Ni 60 days that this precipitation is placed pH
2+Accumulation stripping concentration only be 0.09mg.l
-1
Claims (4)
1, a kind of heavy metal precipitator is N, N-two dithio piperazinecarboxylic acid sodium.
2, a kind of heavy metal precipitator contains 98.5～99 weight %N, N-two dithio piperazinecarboxylic acid sodium and 1～1.5% weight Al
2(SO4)
3Form.
3, a kind of heavy metal precipitator, by 41～93 weight %N, N-two dithio piperazinecarboxylic acid sodium, 5～56 weight % activated carbon powder, 1～1.5 weight %Al
2(SO4)
3Form with 1～1.5 weight %MgSO4.
4, the application of arbitrary heavy metal precipitator in wastewater treatment in the claim 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100513865A CN100345772C (en) | 2004-09-08 | 2004-09-08 | Heavy metal precipitating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100513865A CN100345772C (en) | 2004-09-08 | 2004-09-08 | Heavy metal precipitating agent |
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| Publication Number | Publication Date |
|---|---|
| CN1603249A true CN1603249A (en) | 2005-04-06 |
| CN100345772C CN100345772C (en) | 2007-10-31 |
Family
ID=34665971
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|---|---|---|---|
| CNB2004100513865A Active CN100345772C (en) | 2004-09-08 | 2004-09-08 | Heavy metal precipitating agent |
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| Country | Link |
|---|---|
| CN (1) | CN100345772C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947381A (en) * | 2009-07-08 | 2011-01-19 | 东曹株式会社 | The processing method of heavy metal treatment agent and heavy metal pollution material |
| CN102216410A (en) * | 2008-11-18 | 2011-10-12 | 东曹株式会社 | Solid heavy metal processing agent, method for producing same and use of same |
| CN102432089A (en) * | 2011-11-14 | 2012-05-02 | 浙江至美环境科技有限公司 | Preparation method of broad-spectrum heavy metal trapping agent |
| CN102839042A (en) * | 2012-08-27 | 2012-12-26 | 句容市恒祥金属再生利用有限公司 | Cutting fluid used for grinding high-speed tool steel grinding wheel |
| CN103237796A (en) * | 2010-11-30 | 2013-08-07 | 东曹株式会社 | Aqueous solution of piperazine-N, N'-bis-carbodithioate, and production method for same |
| CN108264138A (en) * | 2018-02-06 | 2018-07-10 | 湖南科技大学 | A kind of copolymerized macromolecule chelated flocculating agent and preparation method thereof |
| CN110526370A (en) * | 2019-09-10 | 2019-12-03 | 上海丰信环保科技有限公司 | The heavy metal chelating agent and preparation method thereof of complex state heavy metal copper in a kind of processing waste water |
| CN112552262A (en) * | 2020-08-13 | 2021-03-26 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN113480082A (en) * | 2021-04-25 | 2021-10-08 | 内蒙古东华能源有限责任公司 | Environment-friendly process for treating coal chemical industry sewage |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465597B2 (en) * | 1981-08-10 | 1997-07-01 | Tetra Tech | Treatment of industrial wastewaters |
| DE3854102T2 (en) * | 1987-05-06 | 1995-12-14 | Agfa Gevaert Nv | Process for processing a photographic material. |
-
2004
- 2004-09-08 CN CNB2004100513865A patent/CN100345772C/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216410A (en) * | 2008-11-18 | 2011-10-12 | 东曹株式会社 | Solid heavy metal processing agent, method for producing same and use of same |
| CN102216410B (en) * | 2008-11-18 | 2014-10-15 | 东曹株式会社 | Solid heavy metal processing agent, method for producing same and use of same |
| CN101947381A (en) * | 2009-07-08 | 2011-01-19 | 东曹株式会社 | The processing method of heavy metal treatment agent and heavy metal pollution material |
| CN101947381B (en) * | 2009-07-08 | 2015-01-28 | 东曹株式会社 | heavy metal treating agent and heavy metal pollutants treating method |
| CN103237796B (en) * | 2010-11-30 | 2015-09-09 | 东曹株式会社 | Piperazine-N, N '-bis-dithionic acid salt brine solution and manufacture method thereof |
| CN103237796A (en) * | 2010-11-30 | 2013-08-07 | 东曹株式会社 | Aqueous solution of piperazine-N, N'-bis-carbodithioate, and production method for same |
| CN102432089A (en) * | 2011-11-14 | 2012-05-02 | 浙江至美环境科技有限公司 | Preparation method of broad-spectrum heavy metal trapping agent |
| CN102839042A (en) * | 2012-08-27 | 2012-12-26 | 句容市恒祥金属再生利用有限公司 | Cutting fluid used for grinding high-speed tool steel grinding wheel |
| CN108264138A (en) * | 2018-02-06 | 2018-07-10 | 湖南科技大学 | A kind of copolymerized macromolecule chelated flocculating agent and preparation method thereof |
| CN110526370A (en) * | 2019-09-10 | 2019-12-03 | 上海丰信环保科技有限公司 | The heavy metal chelating agent and preparation method thereof of complex state heavy metal copper in a kind of processing waste water |
| CN112552262A (en) * | 2020-08-13 | 2021-03-26 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN112552262B (en) * | 2020-08-13 | 2022-03-08 | 成都恒鑫和环保科技有限公司 | Synthesis method of piperazine-N, N' -potassium bisdithio carboxylate |
| CN113480082A (en) * | 2021-04-25 | 2021-10-08 | 内蒙古东华能源有限责任公司 | Environment-friendly process for treating coal chemical industry sewage |
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| Publication number | Publication date |
|---|---|
| CN100345772C (en) | 2007-10-31 |
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Owner name: GUANGDONG ZHONGDA ENVIRONMENTAL SCIENCE AND TECHNO Free format text: FORMER OWNER: ZHONGSHAN UNIV. Effective date: 20100122 |
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