CN1197906C - Heavy metal chelator compound containing chitosan derivative - Google Patents
Heavy metal chelator compound containing chitosan derivative Download PDFInfo
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- CN1197906C CN1197906C CN 03178585 CN03178585A CN1197906C CN 1197906 C CN1197906 C CN 1197906C CN 03178585 CN03178585 CN 03178585 CN 03178585 A CN03178585 A CN 03178585A CN 1197906 C CN1197906 C CN 1197906C
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- heavy metal
- chitosan derivatives
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Abstract
The present invention provides a heavy metal chelate composition with chitosan derivatives. The heavy metal chelate composition of the present invention comprises 1 to 100 wt% of chitosan derivatives with at least one formate disulfide and 0 to 99 wt% of polyamine derivatives with at least one formate disulfide. The heavy metal chelate composition of the present invention is suitable for the treatment of waste water with heavy metal ions or sludge with the heavy metal ions or trash burning fly ash or soil polluted by the heavy metal ions.
Description
Invention field
The invention belongs to field of environment protection, belong to especially and contain harmful heavy metal ion waste or waste water treatment field.
Technical background
Water is the basic substance that the mankind depend on for existence, is the most valuable irreplaceable natural data.Along with The development in society and economy; human demand to fresh water increases sharply; but because the high development of industry; especially the development of mechanical workout, mining, metallurgy and chemical industry; the trade effluent of metal ion also is on the rise to the pollution destruction of water bodys such as river, river, lake, sea; wherein; heavy metal ion such as mercury, lead, cadmium, copper, zinc, manganese, chromium and arsenic have constituted serious harm in different areas, the world to human health, and water resources crisis is perplexing the sustainable development that is restricting many countries and regions society.As far back as the initial stage fifties, the problem of environmental pollution of heavy metal has just caused common concern, and along with the high development of industry, heavy metal ion such as mercury, lead, cadmium, copper, zinc, manganese, chromium, arsenic are serious day by day to the harm of human health.For this reason, people more and more pay close attention to the improvement of heavy metal ion, have proposed multiple improvement method, and wherein most widely used is the chemical settling flocculence, has used a variety of chemical flocs.But this class medicament belongs to chemical such as sodium hydroxide, calcium hydroxide etc. more, and itself will pollute its production process environment, and the sediment instability that contains heavy metal that is produced when administering, and dissolving causes secondary pollution easily.So, stricter standard and standard have been formulated to avoid the pollution of heavy metal ions in wastewater in countries in the world in recent years, the content of metal ion must be lower than the concentration that is allowed in the mandatory requirement waste water, and also proposed various ways removing the metal ion in the waste water, known in this class technology have chemical method (comprising the precipitator method, oxidation reduction process etc.), ion-exchange resin, electrolytic process, absorption method, reverse osmosis method, electrolytic process, evaporation concentration method, a biological process etc.In these methods, belong to the more specific equipment of needs of physics method, bigger energy consumption causes treatment cost significantly to rise, thus generally adopt be still chemical precipitation method, and the form of heavy metal ion with metal hydroxides or sulfide is precipitated out.Because the oxyhydroxide of metal has certain solubleness in water, thus be difficult to all remove metal ion, and the throw out that generates and unstable, the time spent of doing that runs into acid rain etc. still can be partly dissolved, and causes secondary pollution.
One of purpose of the present invention just provides a kind of heavy metal chelant, it can generate stable chelate with the trace heavy metals ion that can't remove with the precipitator method, and energy rapid flocculation sedimentation, thereby from water, separate easily, the inner complex chemical property that is generated is stable, can the secondary degraded not cause new pollution.
On the other hand; quickening along with industrialization and urbanization paces; the danger wastes quantity growth that is produced in human being's production and the life process is surprising; the seriousness that environment is polluted in view of Hazardous wastes; nineteen eighty-three, United Nations Environment Programme (UNEP) was with itself and acid rain; climate warming and ozonosphere protection are listed as global environmental problem; municipal wastes is one of main source of danger wastes; it is the basic countermeasure of administering waste pollution that daily-life garbage without environmental pollution is handled; big for the density of population; the area that concentrate in the city occupies cultivated land for reducing; the protection underground water source tends to substitute garbage loading embeading with waste incineration.In the flying dust that waste incineration produced, be rich in heavy metal, stripping for dangerous composition in the control flying dust, reduce migration and the loss of heavy metal ion in environment, realize minimizing and resource utilization to greatest extent, the stabilization of danger wastes more and more comes into one's own with curing.Solidify the big shortcoming of increase-volume at tradition, the chemical agent stabilization technology is being accelerated research and development.
Another object of the present invention a kind ofly is used for garbage flying ash with regard to providing, contain heavy-metal pollution and carried out the heavy metal chelant composite of the chitosan-containing derivative of stabilization treatment by the soil of heavy-metal pollution, said composition is mixed with the refuse that contains heavy metal ion, make heavy metal and sequestrant chelating in the refuse under certain condition, become and be difficult to the dissolved inner complex, to reach the purpose of harmless treatment, satisfy the requirement that further landfill is disposed.
Description of the invention
More particularly, the purpose of this invention is to provide a kind of waste water and mud that is used to contain heavy metal ion, incineration of refuse flyash and by the heavy metal chelant composite that contains chitosan derivatives of the processing of the soil of heavy-metal pollution.The content of chitosan derivatives is for more than or equal to 1% to equaling 100% (weight percent) in the described composition, is preferably greater than to equal 1% to equaling 25% (weight percent), and all the other compositions are polyamine derivative.It is that major ingredient is produced heavy metal chelant that the present invention adopts by natural renewable resource chitosan derivatives, not only opened up the new purposes of economical rationality for the comprehensive utilization of natural waste, and formed heavy metal chelate chemical property is stable in the treating processes, be easy to immobilization and handle, can not cause secondary pollution.Compare with the external chemosynthesis sequestrant that adopts usually, it is low that goods of the present invention also have price, the advantage that using method is easy.China's crustaceans physical resources are abundant, and enterprise of existing hundreds of family utilizes crust to produce chitin and chitosan, but its application and development is just at the early-stage, utilize the reprocessing of chitin or chitosan to make product of the present invention, do not produce any three wastes material.
Another object of the present invention provides a kind of waste water that is used to contain heavy metal ion and mud, incineration of refuse flyash and by the heavy metal chelant composite that contains chitosan derivatives and polyamine derivative of the processing of the soil of heavy-metal pollution.The capture scope of heavy metal ion has been widened in the composite use of chitosan derivatives and polyamine derivative, has strengthened synergistic effect, has simplified using method, has reduced treatment cost, has improved regulation effect.The %WT meaning is a weight percent in this article.
Collaborative heavy metal chelant composite of the present invention contains following component:
Component concentration %WT
The chitosan derivatives 1-100 that has at least one dithio formate
The polyamine derivative 0-99 that has at least one dithio formate
Preferably, collaborative heavy metal chelant composite of the present invention contains following component:
Component concentration %WT
The chitosan derivatives 1-25 that has at least one dithio formate
The polyamine derivative 75-99 that has at least one dithio formate
Wherein said chitosan derivatives has following general formula I:
General formula I
Wherein:
R:H or
The present invention preferably has the chitosan derivatives of at least one dithio formate, is particularly having the substituent chitosan derivatives of at least one dithio formate on 2 carbon amino of chitosan molecule or on the hydroxyl of 6 carbon.
The said chitosan of the present invention comprises chitosan, oligochitosan or chitin.The said chitosan derivatives of the present invention is meant that molecular weight is more than or equal to 500 chitosan derivatives, oligochitosan derivative or chitin derivativ.
Chitosan derivatives of the present invention can for example prepare like this, by chitosan and dithiocarbonic anhydride in the presence of alkali to the reactive hydrogen on the amino replace the amino of chitosan dithioformate that generates or hydroxyl carried out xanthogenic acid xanthogenate that esterification generates.Described alkali is the carbonate of period of element Table I family basic metal or II family alkaline-earth metal preferably, supercarbonate, hydride, oxyhydroxide, more preferably sodium hydroxide or potassium hydroxide.The chitosan that the present invention is used for preparing chitosan derivatives is meant that molecular weight is greater than 500 chitosan, oligochitosan or chitin.
The polyamine derivative preferred molecular weight of at least one dithio formate that has of the present invention is at the polyamines below 500.The said polyamine derivative that has at least one dithio formate of the present invention is meant and has the substituent polyamines of at least one dithio formate on the amino of polyamines.
Polyamine derivative of the present invention can for example prepare like this, makes the reaction of diamine compounds or polyamine compounds and alkaline aqueous solution, drips dithiocarbonic anhydride again, produces the polyamine derivative that has at least one dithio formate.Described alkaline aqueous solution preferred elements periodictable I family's basic metal or II family alkaline earth metal carbonate, supercarbonate, hydride, the aqueous solution of oxyhydroxide, more preferably sodium hydroxide or potassium hydroxide aqueous solution.
The diamine compounds or the polyamine compounds that are used for preparing polyamine derivative of the present invention comprise aliphatics, alicyclic or aromatic diamine compounds or polyamine compounds.The compound that preferably has following general formula I I:
Wherein: R
2Represent aromatic ring, the aliphatics ring,
N=0,1 integer,
The integer of p=0～10,
The integer of q=1～10000.
Wherein the aromatic series fourth finger has the condensed carbocyclic ring of 6-18 carbon atom or contains the heterocycle that one or more oxygen, nitrogen or sulphur are into ring hetero atom, preferred phenyl ring, and naphthalene nucleus can have one or several substituting group above, methyl for example, hydroxyl, halogen atom etc.Described aliphatics fourth finger has the aliphatics carbocyclic ring of 6-18 carbon atom, preferred cyclopentyl, cyclohexyl, suberyl, ring decyl etc.
Preferably quadrol, diethylenetriamine of the compound of general formula I I wherein, triethylene tetramine, cyclohexanediamine, phenylenediamine, polyethyene diamine etc.
The polyamine derivative that has at least one dithio formate that is generated by the compound of general formula I I has general formula III:
Wherein: R
2Represent aromatic ring, the aliphatics ring,
R
3, R
4And R
5Can be identical or different, represent separately H or
Condition is R
3, R
4And R
5Can not be hydrogen simultaneously.
N=0,1 integer,
The integer of p=0～10,
The integer of q=1～10000.
Wherein said aromatic ring, the definition in the compound of the definition of aliphatics ring and mutual-through type II is identical.
Adopt heavy metal chelant composite of the present invention to handle when containing the waste water of heavy metal ion, an amount of this product can be put in the treatment tank, stir, leave standstill, pollution under the sedimentation leached get final product, use this product is handled flying dust, this product can be sprayed in the flying dust kneader to get final product with abundant kneading of flying dust (adding suitable quantity of water).
Embodiment 1
Take by weighing molecular weight and be about 10000 chitosan 5g, put into the four-hole boiling flask that has reflux exchanger, thermometer, add water 500ml, NaOH 2.5g, stir, be warming up to 35 ℃, drip dithiocarbonic anhydride 5ml again, reacted 3 hours down at 40 ℃, be warming up to 80 ℃, reacted 8 hours, stop heating, reduce to room temperature, reaction product is the aqueous solution of the chitosan that has nabam.Filter, vacuum-drying obtains product.By analysis, this functionality that has the chitosan derivatives of nabam is the 0.63mmol/g chitosan.
Ultimate analysis: S:4.04%
Embodiment 2
Take by weighing molecular weight and be 15000 chitosan 10g, put into the four-hole boiling flask that has reflux exchanger, thermometer, add water 1500ml, KOH2.5g, stir, be warming up to 45 ℃, drip dithiocarbonic anhydride 5ml again, reacted 3 hours down at 40 ℃, be warming up to 80 ℃, reacted 10 hours, stop heating, reduce to room temperature, reaction product is the aqueous solution of the chitosan that has dithiocarbamic acid potassium.Filter, vacuum-drying obtains product.By analysis, this functionality that has the chitosan derivatives of dithiocarbamic acid potassium is the 0.39mmol/g chitosan.
Ultimate analysis: S:2.53%
Embodiment 3
Take by weighing quadrol 60g, put into and have reflux exchanger, in the four-hole boiling flask of thermometer, the NaOH aqueous solution 200ml of adding 20% stirred 30 minutes, dripped dithiocarbonic anhydride 80 grams again, descended anti-3 hours at 40 ℃, be warming up to 50 ℃ of reactions 2 hours again, reduce to room temperature, obtain the aqueous solution, evaporation, drying gets product, through nmr analysis, this product is quadrol two (nabam).
Ultimate analysis: C:24.76%, H:3.05%, N:15.38%, S:32.77%
Embodiment 4
Take by weighing cyclohexanediamine 120g, put into and have reflux exchanger, in the four-hole boiling flask of thermometer, the KOH aqueous solution 400ml of adding 10% stirred 40 minutes, dripped dithiocarbonic anhydride 180 grams again, reacted 4 hours down at 40 ℃, be warming up to 50 ℃ of reactions 2 hours again, reduce to room temperature, obtain the aqueous solution, evaporation, drying gets product, through nmr analysis, this product is cyclohexanediamine two (dithiocarbamic acid potassium).
Ultimate analysis: C:34.15%, H:4.19%, N:10.48%, S:22.68%
Embodiment 5
Take by weighing phenylenediamine 150g, put into and have reflux exchanger, in the four-hole boiling flask of thermometer, the KOH aqueous solution 400ml of adding 10% stirred 120 minutes, dripped dithiocarbonic anhydride 300 grams again, reacted 12 hours down at 45 ℃, be warming up to 55 ℃ of reactions 4 hours again, reduce to room temperature, obtain the aqueous solution, evaporation, drying gets product, through nmr analysis, this product is phenylenediamine two (dithiocarbamic acid potassium).
Ultimate analysis: C:35.15%, H:3.20%, N:11.25%, S:20.31%
Embodiment 6
Take by weighing polyethyene diamine 1200g, put into and have reflux exchanger, in the four-hole boiling flask of thermometer, the NaOH aqueous solution 1500ml of adding 10% stirred 40 minutes, dripped dithiocarbonic anhydride 1800 grams again, reacted 10 hours down at 40 ℃, be warming up to 50 ℃ of reactions 2 hours again, reduce to room temperature, obtain the aqueous solution, evaporation, drying gets product, through nmr analysis, this product is polyethyene diamine two (dithiocarbamic acid potassium).
Ultimate analysis: S:27.65%
Embodiment 7
Get the chitosan derivatives 100mg of embodiment 1 preparation, add water 50ml dilution, make the heavy metal chelant composite diluent, standby.
Get silver-containing waste water 200ml, measuring its silver ion content is 200mg/l, splashes into above-mentioned heavy metal chelant composite diluent 5.0ml, stirs 5 minutes, leaves standstill 30 minutes, filters out precipitation, measures in the filtrate silver ion content once more and reduces to 0.9mg/l.
Embodiment 8
Get the chitosan derivatives 20mg of embodiment 1 preparation, the ethylene diamine derivative 980mg of embodiment 3 preparations adds water 10ml dilution, makes the heavy metal chelant composite diluent, and is standby.
Get silver-containing waste water 200ml, measuring its silver ion content is 200mg/l, splashes into above-mentioned heavy metal chelant composite diluent 1.0ml, stirs 5 minutes, leaves standstill 30 minutes, filters out precipitation, measures in the filtrate silver ion content once more and reduces to 0.7mg/l.
Embodiment 9
Getting the chitosan derivatives 1.0g of embodiment 2 preparation, is 7% with chitosan derivatives weight percent content wherein, and the phenylenediamine derivative weight percent content is that 93% ratio adds phenylenediamine two (dithiocarbamic acid potassium), adds water 10ml dilution, and is standby.
Get incineration of refuse flyash 100g, measure wherein that lead content is 500ppm, zinc 300ppm, copper 120ppm, cadmium 100ppm gets flying dust 50g and adds entry 5ml, heavy metal chelant composite diluent 5ml, fully stir, mediated 20 minutes, as specimen, 50g flying dust sample in contrast in addition, carry out dissolution test according to U.S. TCLP standard respectively, use the Atomic Absorption Spectrometry heavy metal content, measurement result sees Table:
| Metal stripping quantity (ppm) | ||||
| Plumbous | Zinc | Copper | Cadmium | |
| Specimen | 0.5 | 0.4 | Do not detect | Do not detect |
| Control sample | 25 | 11.5 | 0.5 | 0.2 |
Embodiment 10
Get the chitosan derivatives 0.6g of embodiment 1 preparation, with chitosan derivatives weight percent content wherein is 14%, the polyethylenimine derivates weight percent content is 86% ratio adding polyethyene diamine two (dithiocarbamic acid potassium), adds water 10ml dilution, and is standby.
Get certain nickel-containing waste water 200ml of Electroplate Factory, measure wherein that nickel content is 123ppm, add above-mentioned heavy metal chelant composite diluent 1.2ml, stirred 5 minutes, left standstill 30 minutes, remove by filter sediment, measure in the filtrate nickel content and reduce to 2.8ppm.
Embodiment 11
Get heavy metal chelant composite 10ml of the present invention, wherein the chitosan derivatives content of embodiment 2 preparations is 65% (weight), and cyclohexanediamine two (dithiocarbamic acid potassium) content is 35% (weight), and it is standby to be diluted to 100ml with deionized water.
Getting lead content is 174ppm, and the pH value is that 4.5 aqueous solution sample 200ml puts into beaker, adds above-mentioned composition diluent 1.5ml, stirs 5 minutes, and stopping can to observe in 2 seconds after the stirring has a large amount of black throw outs to settle down with interior.Leave standstill 30 minutes after-filtration, filtrate clarification water white transparency, through the atomic absorption spectrophotometer analysis, wherein plumbum ion concentration is reduced to 0.1ppm.
Embodiment 12
Get the chitosan derivatives 100mg of embodiment 1 preparation, the ethylene diamine derivative 2mg of embodiment 3 preparations adds water 10ml dilution, makes the heavy metal chelant composite diluent, and is standby.
Get silver-containing waste water 200ml, measuring its silver ion content is 200mg/l, splashes into above-mentioned heavy metal chelant composite diluent 1.0ml, stirs 5 minutes, leaves standstill 30 minutes, filters out precipitation, measures in the filtrate silver ion content once more and reduces to 0.9mg/l.
Claims (3)
1. heavy metal chelant composite that contains chitosan derivatives, it is characterized in that said composition contains: 1-100wt% is having the substituent chitosan derivatives of at least one dithio formate on the amino of 2 carbon atoms on all sugar rings of chitosan molecule or on the hydroxyl of 6 carbon atoms, with 0-99wt% on the amino of polyamines, have a substituent polyamines of dithio formate at least, wherein said chitosan derivatives has general formula I:
Wherein
R:H or
X:Na, K, NH
4, 1/2Ca, or 1/2Mg,
The integer of m:10～100000,
R and R
1Can not be hydrogen simultaneously;
Wherein said polyamine derivative has general formula III:
Wherein: R
2Represent aromatic ring, the aliphatics ring,
R
3, R
4And R
5Can be identical or different, represent H separately, or
X:Na, K, NH
4, 1/2Ca, or 1/2Mg,
Condition is R
3, R
4And R
5Can not be hydrogen simultaneously,
N=0,1 integer,
The integer of p=0～10,
The integer of q=1～10000.
2. according to the composition of claim 1, wherein said chitosan derivatives is meant that molecular weight is greater than 500 chitosan derivatives.
3. claim 1 or 2 heavy metal chelant composite are used to contain the waste water and the mud of heavy metal ion, incineration of refuse flyash or by the purposes of the processing of the soil of heavy-metal pollution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03178585 CN1197906C (en) | 2002-07-24 | 2003-07-23 | Heavy metal chelator compound containing chitosan derivative |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02125605A CN1389502A (en) | 2002-07-24 | 2002-07-24 | Heavy metal chelant composite containing chitosan derivative |
| CN02125605.5 | 2002-07-24 | ||
| CN 03178585 CN1197906C (en) | 2002-07-24 | 2003-07-23 | Heavy metal chelator compound containing chitosan derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1495225A CN1495225A (en) | 2004-05-12 |
| CN1197906C true CN1197906C (en) | 2005-04-20 |
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|---|---|---|---|
| CN 03178585 Expired - Fee Related CN1197906C (en) | 2002-07-24 | 2003-07-23 | Heavy metal chelator compound containing chitosan derivative |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI400250B (en) * | 2009-08-28 | 2013-07-01 | Univ Nat Kaohsiung 1St Univ Sc | Process for preparing chitosan particles and method for adhesion of the same to chelator |
| CN101816958B (en) * | 2010-02-05 | 2012-02-01 | 北京欧凯纳斯科技有限公司 | Application of chelate type chemical modified chitosan in removing heavy metal ions in plant juicechelate |
| CN101817887B (en) * | 2010-02-05 | 2012-03-28 | 北京欧凯纳斯科技有限公司 | Chelation group-containing chitosan and preparation method and application thereof |
| CN101885786B (en) * | 2010-06-04 | 2012-03-28 | 北京欧凯纳斯科技有限公司 | Chelation group-containing chitosan and preparation method and application thereof |
| CN102718888A (en) * | 2011-11-24 | 2012-10-10 | 中国科学院海洋研究所 | Novel dithiocarbamate derivative of chitosan and preparation method thereof |
| CN104119923B (en) * | 2013-04-25 | 2016-12-28 | 成都新朝阳作物科学有限公司 | Heavy metal-polluted soil renovation agent and application thereof |
| CN103804091A (en) * | 2014-02-21 | 2014-05-21 | 湖南大学 | Nutrition modifier rich in selenium for lowering content of heavy metals in food crops and application thereof |
| CN106824119A (en) * | 2017-04-01 | 2017-06-13 | 兰州交通大学 | A kind of xanthogenation shitosan and preparation method thereof |
| CN108486199B (en) * | 2018-03-27 | 2020-12-22 | 北京中科众联新能源技术服务有限公司 | Water-soluble chelating agent, preparation method thereof and heavy metal wastewater treatment method using water-soluble chelating agent |
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2003
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