CN1069008A - Utilize thiamine disulfide chelating agent to handle the method for heavy metal in the waste water - Google Patents
Utilize thiamine disulfide chelating agent to handle the method for heavy metal in the waste water Download PDFInfo
- Publication number
- CN1069008A CN1069008A CN 91105361 CN91105361A CN1069008A CN 1069008 A CN1069008 A CN 1069008A CN 91105361 CN91105361 CN 91105361 CN 91105361 A CN91105361 A CN 91105361A CN 1069008 A CN1069008 A CN 1069008A
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- heavy metal
- waste water
- chelating agent
- thiamine disulfide
- handle
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Abstract
The invention relates to a kind of method of utilizing thiamine disulfide chelating agent to handle heavy metal in the waste water, at length say it is to utilize a kind of thiamine disulfide chelating agent and various heavy metal ions in waste water to form inner complex to precipitate and remove.Method provided by the present invention can produce heavy metal ion such as the copper in the waste water, nickel, cadmium, lead, manganese, cobalt, iron, zinc and sexavalent chrome fast precipitation and remove.
Description
The present invention is relevant a kind of method of utilizing thiamine disulfide chelating agent to handle heavy metal in the waste water, especially refer to a kind of method of utilizing the heavy metal in the flowing water that the thiamine disulfide based compound removes the discharging of general industry and mining factory, be subjected to the pollution of heavy metal again to avoid the coastal and soil in streams, present rivers and creeks.
Environment protection is the current first heavy hot issue of modernization country, because, with the work industrial progress; though improve the human living standard; but the heavy industry that it brought is polluted, and will involve universe's living space in future, this main cause that also why worldwide environmental protection organization constantly enlarges just.
Multiple with domestic sight it, with the acceleration of work economic reform, attract foreign trader or Tianwan businessman's investment, make various factory stand in great numbers, this phenomenon in the ascendant, constantly progressive and jump to the woods of progressive country except that proof motherland, brought the heavy industry pollution problem also in an instant.Because the quick continually numerous life of factory, the pollution that various plant effluent discharging causes with the considerable damage environmental ecology, and then influences future living space.But be not the attention of relevant authorities yet at present.
According to research, the waste water of general factory discharging all contains the heavy metal of a large amount, and for example heavy metal ion, these type of heavy metal ion such as copper, nickel, cadmium, lead, manganese, cobalt, iron, zinc and sexavalent chrome are the source of pollution.After this type of waste water that contains heavy metal flows into the water source, will make agricultural-food or drinking-water involve pollution, fearful pathology can take place in edible back in human body, and this type of case once took place in place, many places, the world, influenced extremely hugely, was necessary to be on one's guard.For taking precautions against in possible trouble, the method that whether can provide a kind of high-level efficiency to handle the heavy metal in the waste water, ensureing compatriots' health, the main category that will probe into for the present invention.
The at present general method of handling the heavy metal waste liquid is for utilizing chemical deposition method, promptly under the pH value is about 10 situation, and adding iron trichloride (FeCl
3) be used as flocculation agent, and add the polymer coagulant aids to quicken to remove the heavy metal in the waste liquid.
Though utilize above-mentioned treatment process can effectively remove some metal ion, can't fully the heavy metal in the waste liquid be removed.Therefore, this effect is unsatisfactory, and space, time and funds cost required when handling are all very big, so and be not suitable for present midget plant and use, the waste water of the metal ion of some formation inner complexs still can't solve (explanation of consulting following examples II) so far still more.
Above-mentioned described method must have very big space and environment, consumes immeasurablely on cost and funds, does not meet economic benefit.
Therefore, requisite space is little when looking for a kind of both rapidly convenient and processing, and the cheap treatment technology of funds cost is that the purpose of asking is desired to reach by creation motivation of the present invention and institute.
Method of the present invention is to utilize various heavy metal ion in thiamine disulfide chelating agent and the effluent discharge to form the inner complexs precipitation and remove heavy metal in the waste water; Wherein the structural formula of employed thiamine disulfide chelating agent is broadly divided into two kinds:
R wherein, R ' is H, C
nH
2n+1, C
nH
2n-1Or C
nH
2n, and X
+Be Na
+, K
+, NH
+ 4Deng positively charged ion; Or be
Wherein, R, R ' are H, C
nH
2n+1, C
nH
2n-1Or aryl, and n=2-6 or polyallylamine (Polyallylamine, M.W. 60000 with interior all can), and X
+Be Na
+, K
+, NH
+ 4Deng positively charged ion.
X in the above-mentioned two big class sequestrants
+Be the different alkali that is added by in the preparation sequestrant process, as NaOH, NH
4OH or KOH deutero-, its purpose are to make said sequestrant energy soluble in water.
In addition, in thiamine disulfide chelating agent of the present invention and the waste water heavy metal to form the structure of sedimentary inner complex as follows:
Wherein, the definition of R and R ' and n is the same, and M is a transition metal.
This inner complex that forms is insoluble or only be slightly soluble in compound in the water, therefore can smoothly the heavy metal element in the waste water be precipitated fully to leach.
If adopt above-mentioned method, can make things convenient for and the fast processing waste liquid in heavy metal, make it form inner complex precipitation, and finish effective processing waste liquid.So use method of the present invention can prevent pollution of waterhead, dwindle required processing space environment and time, and reduce cost.
Treatment step of the present invention comprises and places one to mix groove the heavy metal waste liquid, adds thiamine disulfide based compound stir about after 20 minutes, and throw out is made its natural sedimentation with strainer or natural modes of emplacement.
The usage quantity for the treatment of processes reagent is decided by the concentration of pending waste liquid contained heavy metal total concn to which kind of degree and the waste liquid.Under normal condition, as only containing the copper of single ionic in the waste liquid, the about 10mg/l of its concentration, if when desire is removed to 3mg/l standard (environmental protection unit fixed standard), then approximately must be with 2.5 liters agent treated in 1000 liters the waste liquid.
When if pending liquid waste concentration is the lead of 1.0mg/l or cadmium, its used amount of reagent is still identical, only its formed particle is less, so as the polymer coagulant aids or the placement that add 5mg/l spend the night, can remove heavy metal when refiltering and reach environmental protection unit within the fixed standard range.
The thiamine disulfide chelating agent of the present invention preparation be utilize the diamine organic matter of equivalent and dithiocarbonic anhydride low temperature (0～20 ℃) stir down with stoichiometric number hour after, the basic solution that slowly adds equivalent makes it neutralization, make temperature recovery to room temperature state again, and then separate unreacted dithiocarbonic anhydride, and be diluted to optimum quantum of utilization concentration.This reagent produces white solid and reacted solution can be poured into as will make the reagent that forms solid shape the time in alcohol or the acetone soln, the solid part that filters the back gained is thiamine disulfide chelating agent.
Below, be according to method provided by the present invention and the test verification of respectively waste water of the heavy metal that contains heterogeneity being done, wherein the sequestrant of the employed thiamine disulfide of embodiment I～IV is aforementioned structural formula (A) sequestrant, its molecular formula can be C
5H
10NS
2Na, working concentration are the 10%(w/w) reagent, and the test of the effect of the structural formula of other differing molecular formulas (A) sequestrant shows: when this reagent is added in the waste liquid that contains heavy metal, also produce the precipitation of inner complex rapidly.Though as seen molecular formula is different, it is as the used reagent of embodiment, and is very good to the removal effect of heavy metal in the waste water.Employed sequestrant is aforementioned structural formula (B) class sequestrant in embodiment V and the VI in addition, and its molecular formula can be C
4H
6N
2S
4Na
2, and concentration also is the 10%(w/w) reagent, and the test of the sequestrant effect of the structural formula of other differing molecular formulas (B) also shows: when this reagent is added in the waste liquid that contains heavy metal, the fast generation inner complex precipitation of result's speed.Though as seen molecular formula is different, reagent used among its ability of removing heavy metal and the embodiment is the same very good.
The embodiment I
Contain the about 10mg/l of copper in the waste water that plating factory discharges, the about 15mg/l of nickel adds concentration 10%(W/W through getting the 200ml waste liquid), molecular formula is C
5H
10NS
2The thiamine disulfide chelating agent of Na, then there is precipitation to produce rapidly, through stir made precipitation fully in 20 minutes after, allow throw out deposit, to filter, and get upper water solution, utilize the content of heavy metal in the Atomic Absorption Spectroscopy AAS test upper water solution, following result is the result when adding the reagent of different volumes.
| Reagent volume | Copper | Nickel |
| 0.5ml | 3.3 | 14 |
| 1ml | 0.7 | 12 |
| 2ml | ND | 8 |
(concentration: mg/l)
ND: the value that content can be surveyed less than instrument
The embodiment II
In general plant effluent, the pH value of its waste water is about 10, contains copper 27.5mg/l and nickel 7.5mg/l in this waste water, this waste liquid is because of containing excess of ammonia, and forms the cuprammonium title complex, and can't be again removes heavy metal in the waste liquid with general fashion, but as adding concentration is 10%(W/W), molecular formula is C
5H
10NS
2During the thiamine disulfide base sequestrant of Na, then precipitation produces rapidly, refilters after allowing precipitation fully in 20 minutes through stirring, and the aqueous solution is tested with Atomic Absorption Spectroscopy AAS, and its result is as follows:
| Reagent volume | Copper | Nickel |
| 5ml | 0.01 | 0.06 |
The embodiment III
Be further to understand the treatment effect of this type of reagent to all kinds of heavy metals, inventor's preparation respectively contains six kinds of elements such as the copper, lead, nickel, manganese, cobalt, cadmium of 10mg/l, adds different volumes and concentration is 10%(W/W), molecular formula is C
5H
10NS
2The thiamine disulfide base sequestrant of Na and make it produce precipitation, the sample of same concentration also utilizes the mode of commonly using to handle, operating method is 45% for slowly going into concentration, volume is the sodium hydroxid of 25ml, make it produce precipitation, behind the filtering-depositing, utilize Atomic Absorption Spectroscopy AAS test upper water solution the content of surplus each heavy metal species, its result following (wherein the volume of the sample of handling is 200ml):
| Concentration is 10%(W/W) molecular formula is C 5?H 10?HS 2The thiamine disulfide agent treated result of Na | Reagent volume | Copper | Nickel | Manganese | Plumbous | Cadmium | Cobalt |
| 1ml 2ml 4ml | 0.31 0.03 ND | 9.0 3.2 0.3 | 10 9 0.3 | 1.2 0.8 0.2 | 4.5 3.6 0.02 | 6.0 2.2 ND | |
| According to commonly using mode, utilize 45% NaOH alkali lye result | 25ml | 2.8 | 0.3 | 0.3 | 1.6 | 0.35 | 0.26 |
ND: the value that content can be surveyed less than instrument
The embodiment IV
For testing reagent of the present invention to heavy metal treatment effect more difficult and that concentration is not really high, the inventor prepares cadmium and the lead solution of 10mg/l, gets the sample of 200ml respectively, and adding 1ml concentration is 10%(W/W), molecular formula is C
5H
10NS
2The thiamine disulfide chelating agent of Na adds the fashionable very fine grain precipitation of white that then produces, and after stirring 20 minutes, is convenient and filters, this sample is placed to spend the night refilter, the water intaking solution testing its remaining heavy metal content, its result is as follows:
| Cadmium remnants | 0.32mg/l |
| Plumbous remaining | 0.16mg/l |
Hexavalent chromium (Cr in the waste water
+ 6), it is a kind of ion that is quite difficult to get along and manages and have severe toxicity, in general traditional wastewater treatment at present, also do not have a kind of easy and rapidly treatment process got rid of, and the method for utilizing the present invention to handle with thiamine disulfide base sequestrant, the pH value of waste water is controlled at 1.6～2.5 between adding thiamine disulfide base sequestrant, when making waste water ph after the processing in 7.2, then can precipitate the hexavalent chromium in the waste water, effect will be quite good; If when having other ions to exist jointly in the waste liquid, will make treatment effect more good.
Below illustrate with embodiment:
The embodiment V
Get 50 milliliters of pH values and be 1.8, concentration is the waste water of the hexavalent chromium of 100mg/l, add different volumes, but concentration is 10%(W/W), molecular formula is C
4H
6N
2S
4Na
2Thiamine disulfide chelating agent the time, then produce precipitation rapidly, through stirred 20 minutes and placed spend the night and filter after, test chromic remaining quantity with the upper strata aqueous solution, found that its remaining chromic content is except outside the Pass having with amount of reagent, also relevant with the pH-value of handling the back water sample, its result is as follows:
| Reagent volume | Residual volume (mg/l) | Handle the pH value of back water sample |
| 1ml 2ml 3ml | 41.8 1.6 6.3 | 6.0 7.2 7.9 |
The embodiment VI
Get 50 milliliters of pH values and be 2.0 waste water, it contains copper, iron, zinc, nickel, cadmium, cobalt, manganese, plumbous each 10mg/l, and sexavalent chrome 5mg/l, adds different volumes but concentration is 10%(W/W), molecular formula is C
2H
6N
2S
4Na
2Thiamine disulfide chelating agent, its treatment step as previously mentioned, its result and to handle the pH-value of back water sample as follows:
| Reagent volume | Cu | Fe | Zn | Ni | Cd | Pb | Mn | Co | Cr | Handle the pH value of back water sample |
| 2ml 4ml 6ml 8ml | 0.016 0.115 0.121 0.139 | 0.044 0.022 0.022 0.044 | 0.023 0.068 0.068 0.032 | ND 0.941 0.941 1.000 | 0.523 0.044 0.044 0.044 | ND 0.05 ND 0.05 | 10.0 5.3 0.4 1.7 | 0.015 0.030 0.222 0.603 | 0.05 0.15 0.30 0.75 | 7.2 8.5 9.2 10.0 |
ND: the value that content can be surveyed less than instrument
For sequestrant, the various embodiments described above with structural formula (A) or a kind of compound (B) be the example explanation, structural formula (A) and thiamine disulfide chelating agent (B) to other various differing molecular formulas, the contriver is also to test, to prove the effect that has heavy metal in the same removal waste water equally with the method for embodiment I-VI.In addition, for the sequestrant concentration that is adopted, though in implementing, be as the criterion with 10%, but when adopting treatment process of the present invention, the concentration of this reagent there is no strict demand, during as the processing same sample, use the concentration of reagent rarer, then its reagent usage quantity increases relatively, indicates hereby.
We can find out significantly from above-mentioned, if according to the inventive method, then can be in industry and mining factory, with less space environment and than short time and less funds, utilize the thiamine disulfide based compound can effectively remove heavy metal in the waste water, have utility value on the industry.
Claims (4)
1, a kind of method of handling heavy metal in the waste water, this method comprise thiamine disulfide chelating agent are added in the waste water, form the heavy metal chelate precipitation, with precipitate and separate; The structural formula of said thiamine disulfide chelating agent is:
R wherein, R ' is C
nH
2n+1, C
nH
2n-1Or C
nH
2n, and X
+Be Na
+, K
+, NH
+ 4Deng positively charged ion; Or be
Wherein, R, R ' are H, C
nH
2n+1, C
nH
2n-1Or aryl, n=2～6 or allylamine (Polyallylamine, M.W. 60000 with interior all can), and X
+Be Na
+, K
+, NH
+ 4Deng positively charged ion.
2, according to the process of claim 1 wherein that the sequestrant that uses is that molecular formula is C
5H
10NS
2The thiamine disulfide chelating agent of Na.
3, according to the process of claim 1 wherein that the sequestrant that uses is that molecular formula is C
4H
6N
2S
4Na
2Thiamine disulfide chelating agent.
4, according to the process of claim 1 wherein X
+Be NaOH, the NH that is added by in the preparation sequestrant process
4The alkali deutero-that OH or KOH are different.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105361 CN1025670C (en) | 1991-07-30 | 1991-07-30 | Method for treating heavy metal in waste water utilizing thiamine disulfide chelating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105361 CN1025670C (en) | 1991-07-30 | 1991-07-30 | Method for treating heavy metal in waste water utilizing thiamine disulfide chelating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069008A true CN1069008A (en) | 1993-02-17 |
| CN1025670C CN1025670C (en) | 1994-08-17 |
Family
ID=4907108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91105361 Expired - Fee Related CN1025670C (en) | 1991-07-30 | 1991-07-30 | Method for treating heavy metal in waste water utilizing thiamine disulfide chelating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025670C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818135B2 (en) | 2001-08-03 | 2004-11-16 | Canadus Technologies Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| CN100384528C (en) * | 2005-03-02 | 2008-04-30 | 江苏工业学院 | Novel high effective noble metal adsorbent and its preparing method |
| CN1995015B (en) * | 2006-01-06 | 2010-11-10 | 深圳市危险废物处理站 | Method for preparing feed grade methionine copper chelate using waste etching liquor |
| CN102145946A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN101081807B (en) * | 2006-05-29 | 2012-12-19 | 天津美茵医药科技有限公司 | Method for improving cleanliness of electron chemicals |
| CN104495998A (en) * | 2014-12-18 | 2015-04-08 | 淄博金鼎光电科技有限公司 | Method for synthesizing heavy metal chelating agent |
| RU2590537C1 (en) * | 2015-02-05 | 2016-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет путей сообщения" (ФГБОУ ВО ИрГУПС) | Use of poly(3-oxapentylenedisulphide) for extraction of heavy metals from aqueous solutions |
| CN109568872A (en) * | 2018-10-15 | 2019-04-05 | 宝武集团环境资源科技有限公司 | A kind of method of Cr VI in processing solid waste |
| CN110117240A (en) * | 2018-02-07 | 2019-08-13 | 华东师范大学 | Thiamine disulfide class compound and its synthetic method and application |
-
1991
- 1991-07-30 CN CN 91105361 patent/CN1025670C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818135B2 (en) | 2001-08-03 | 2004-11-16 | Canadus Technologies Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| US6843923B2 (en) | 2001-08-03 | 2005-01-18 | Canadus Technologies Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| US6855259B2 (en) | 2001-08-03 | 2005-02-15 | Canadus Technologies Llc | Process for reducing the passive layer from the surface of a metal |
| US7109366B2 (en) | 2001-08-03 | 2006-09-19 | Canadus Technologies Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| US7163634B2 (en) | 2001-08-03 | 2007-01-16 | Riva Morton, legal representative | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
| CN100384528C (en) * | 2005-03-02 | 2008-04-30 | 江苏工业学院 | Novel high effective noble metal adsorbent and its preparing method |
| CN1995015B (en) * | 2006-01-06 | 2010-11-10 | 深圳市危险废物处理站 | Method for preparing feed grade methionine copper chelate using waste etching liquor |
| CN101081807B (en) * | 2006-05-29 | 2012-12-19 | 天津美茵医药科技有限公司 | Method for improving cleanliness of electron chemicals |
| CN102145946A (en) * | 2011-02-21 | 2011-08-10 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN102145946B (en) * | 2011-02-21 | 2013-06-26 | 中国科学院生态环境研究中心 | Method for treating trace amount of cadmium in wastewater by chelation, coagulation and ultrafiltration combination |
| CN104495998A (en) * | 2014-12-18 | 2015-04-08 | 淄博金鼎光电科技有限公司 | Method for synthesizing heavy metal chelating agent |
| RU2590537C1 (en) * | 2015-02-05 | 2016-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет путей сообщения" (ФГБОУ ВО ИрГУПС) | Use of poly(3-oxapentylenedisulphide) for extraction of heavy metals from aqueous solutions |
| CN110117240A (en) * | 2018-02-07 | 2019-08-13 | 华东师范大学 | Thiamine disulfide class compound and its synthetic method and application |
| CN109568872A (en) * | 2018-10-15 | 2019-04-05 | 宝武集团环境资源科技有限公司 | A kind of method of Cr VI in processing solid waste |
| CN109568872B (en) * | 2018-10-15 | 2021-08-03 | 宝武集团环境资源科技有限公司 | Method for treating hexavalent chromium in solid waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1025670C (en) | 1994-08-17 |
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