CN108017136A - A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter - Google Patents

A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter Download PDF

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Publication number
CN108017136A
CN108017136A CN201711340997.5A CN201711340997A CN108017136A CN 108017136 A CN108017136 A CN 108017136A CN 201711340997 A CN201711340997 A CN 201711340997A CN 108017136 A CN108017136 A CN 108017136A
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CN
China
Prior art keywords
organic matter
sludge
poisonous
changed
trivalent chromium
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Pending
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CN201711340997.5A
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Chinese (zh)
Inventor
魏利
赵云发
张玉华
陈光浩
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Guangzhou HKUST Fok Ying Tung Research Institute
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Guangzhou HKUST Fok Ying Tung Research Institute
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Priority to CN201711340997.5A priority Critical patent/CN108017136A/en
Publication of CN108017136A publication Critical patent/CN108017136A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

Abstract

A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter, is related to a kind of method that poisonous Cr VI is changed into trivalent chromium.The present invention causes secondary pollution to solve the problems, such as that the method removal rate of Cr VI poisonous in existing removal waste water, sludge or soil is low and can produce a large amount of sludge or sediment.Method:To containing Cr6+Waste water in add organic matter, control pH=4~8, react 30~60 minutes;Or by organic matter and contain Cr6+Soil or contain Cr6+Sludge mixing, then add domestic sludge, control pH=4~8, react 60~120 minutes.The present invention will have virose Cr using biological inhibition method6+Fast transition is Cr3+, Cr6+Transition process safety and environmental protection, positive effect, the conversion of the quick valence state for realizing heavy metal chromium, do not cause secondary pollution, cost is only low.The present invention is suitable for poisonous Cr VI being changed into trivalent chromium.

Description

A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter
Technical field
The present invention relates to a kind of method that poisonous Cr VI is changed into trivalent chromium.
Background technology
Heavy metal is widely applied in different application fields and plays an important role, and adding metal ion can be big The big performance for improving material, contains a certain amount of chromium etc. to improve its intensity as in the material of aircraft if, metal surface chromium plating with Increase corrosion resistance etc., under rapid industrial development background, more and more waste water rich in heavy metal are by directly or indirectly It is discharged into environment, the polluter being discharged into environment is more and more.Mankind's activity is to cause the master of heavy metal pollution of water body Reason is wanted, and the below standard discharge of commercial metal waste water and any discharge are most important reasons, wherein mining, ore dressing, smelting The effluent containing heavy metal ions pollution of the generations such as gold, plating, chemical industry, process hides and paper industry is especially serious, what these industry produced The heavy metal wastewater therebies such as mercurous, chromium, cadmium, nickel, copper, lead have larger toxicity, and Heavy Metals in Waters is with quite high steady Qualitative and refractory organics, and can Transport And Transformation etc., difficulty of governance is big, and in water the heavy metal ion of low concentration just have compared with High toxicity, can form aquatile larger threat, and therefore, Heavy Metals in Waters pollutes the ring for having become global concern Border problem.According to correlation study, rivers,lakes and seas of the China more than eighty per cant are faced with heavy metal pollution, and local water pollution Especially severe.National electroplating industry about discharges 400,000,000 tons of waste water containing heavy metal every year according to incompletely statistics, electroplates garden waste water water Matter is complicated, and intractability is big, of high cost, and managed operation mechanism reduces cost from every side, and wastewater treatment is not often up to standard.Plating Containing substantial amounts of soda acid, oil, organic matter, heavy metal ion and cyanide etc. in waste water, current many government departments are also carrying out The theory of electroplating enterprise " concentrate and build, concentrate pollution treatment ".
Cr VI (Cr6+) be easy to be absorbed by the body by skin, digestive system etc., Cr VI toxicity is larger, stimulates skin Cause allergy, and can cause damage to respiratory system and internal organ;In existing removal waste water the method for Cr VI include flocculence, Chemical precipitation method or ferrite process etc.;Flocculence is to form colloid in water using flocculant such as aluminum sulfate, adsorbs underwater gold category Precipitation is formed after ion, so that heavy metal ion be removed from water, this method cost is relatively low, precipitates easily dehydration, shortcoming is meeting A large amount of sludge are produced, consumption of chemical agent is more, and the removal rate of heavy metal is low, and removal rate is about 30%;Chemical precipitation method is to pass through Chemical reaction makes to be changed into heavy metal compound precipitation not soluble in water in waste water in the heavy metal of dissolved state, so that will a huge sum of money Belong to ion to remove from water, common chemical precipitation method has neutralization precipitation method, sulphide precipitation and ferrite process.It is heavy with chemistry The chemical drugs dosage that shallow lake method makes heavy metal ion content in water reach discharge standard needs is more, while can produce a large amount of sludge, Make its processing cost high.Ferrite process is by adding molysite into waste water, by controlling process conditions, makes the huge sum of money in waste water Category ion enters in ferrite lattice under ferritic parcel, entrainment effect forms complex ferrite, then passes through solid-liquid point From the method for removing heavy metal ion from water.Ferrite process is divided into two kinds of neutralisation and oxidizing process, and neutralisation is to add Fe2+Afterwards, ferrite is formed with alkali neutralization, and oxidizing process is to add Fe2+Afterwards by being aerated Fe2+Oxidation, so as to form iron oxygen Body.But this method can produce a large amount of sediments, cause to produce secondary pollution.
The content of the invention
The present invention in order to solve the method removal rate of Cr VI poisonous in existing removal waste water, sludge or soil it is low with And the problem of a large amount of sludge or sediment cause secondary pollution can be produced, proposition is a kind of to be changed poisonous Cr VI using organic matter For the method for trivalent chromium.
Poisonous Cr VI is changed into the method for trivalent chromium by the present invention using organic matter, this method according to the following steps into OK:
To containing Cr6+Waste water in add organic matter, control pH=4~8, react 30~60 minutes, that is, complete;
Cr in the waste water6+The BOD concentration (mg/mL) that provides of concentration (mg/mL) and useless Organic substance in water than being 1:(2 ~6);
The organic matter is one or more mixtures in any proportion in glucose, white granulated sugar, sucrose or ethanol.
The principle of the present invention is:
The present invention utilizes biological inhibition method, by the virose Cr of the tool contained in waste water6+Fast transition is nontoxic Cr3 +, solve Cr6+The problem of pollution, concrete principle are:The organic matter that the present invention uses for small molecule organic matter, in waste water Microorganism itself carries negative electrical charge, and the organic matter of small molecule provides carbon source for microbial metabolism, itself is carried after microbial metabolism Negative electrical charge and Cr6+By Cr with reference to after6+It is reduced to Cr3+, realize the conversion of the valence state of heavy metal Cr, have virose Cr6+Quickly It is changed into nontoxic Cr3+
The present invention possesses following beneficial effect:
1st, the present invention will have virose Cr using biological inhibition method6+Fast transition is Cr3+, Cr6+Transition process safety Environmental protection, positive effect, the conversion of the quick valence state for realizing heavy metal chromium, the processing of the heavy metal Cr suitable for waste water, is reduced Cr6+The harm brought to environment, and processing procedure does not produce extra sludge or sediment, avoids causing secondary pollution;
2nd, the method for the present invention can be by virose Cr6+It is completely reformed into Cr3+, equivalent to the removal rate for having reached 100%;
3rd, the existing method for removing Cr VI poisonous in waste water has used substantial amounts of chemical agent, and the present invention only uses Lower-cost glucose, white granulated sugar, sucrose or ethanol etc., the cost of medicament is only flocculence, chemical precipitation method or iron oxygen The 5~10% of body method.
Poisonous Cr VI is changed into the method for trivalent chromium by the present invention using organic matter, this method according to the following steps into OK:
By organic matter and contain Cr6+Soil or contain Cr6+Sludge mixing, then add domestic sludge, control pH= 4~8, react 60~120 minutes, that is, complete;
The Cr included in the soil or sludge6+Mass content (mg/kg) and soil or the organic matter in sludge matter The ratio for measuring content (mg/kg) is 1:(3~7);
The quality of the domestic sludge and the mass ratio of organic matter are 1:(0.95~1.2);
The organic matter is glucose, white granulated sugar, sucrose, ethanol, glucose solution, white sand sugar aqueous solution or sucrose water One or more mixtures in any proportion in solution.
The principle of the present invention is:
The present invention utilizes biological inhibition method, the virose Cr of tool that will contain in soil or sludge6+Fast transition is Cr3 +, solve Cr6+The problem of pollution, concrete principle are:The organic matter that the present invention uses is the organic matter of small molecule, soil or dirt Microorganism itself in mud carries negative electrical charge, and the organic matter of small molecule provides carbon source for microbial metabolism, after microbial metabolism certainly The negative electrical charge and Cr that body carries6+By Cr with reference to after6+It is reduced to Cr3+, realize the conversion of the valence state of heavy metal Cr, tool is virose Cr6+Fast transition is nontoxic Cr3+;The present invention, which adds domestic sludge, can improve the flocculating effect of soil or sludge, make soil Or sludge is preferably complexed Cr6+, and then make Cr6+Reduction reaction is more abundant, while domestic sludge can also provide various bacteria, It can realize and quickly utilize organic matter, accelerate reaction process.
The present invention possesses following beneficial effect:
1st, the present invention will have virose Cr using biological inhibition method6+Fast transition is Cr3+, Cr6+Transition process safety Environmental protection, positive effect, the conversion of the quick valence state for realizing heavy metal chromium, suitable for the processing of soil or the heavy metal Cr of sludge, Reduce Cr6+The harm brought to environment, and processing procedure does not produce extra sludge or sediment, avoids causing secondary dirt Dye;
2nd, the method for the present invention can be by virose Cr6+It is completely reformed into Cr3+, equivalent to the removal rate for having reached 100%;
3rd, the existing method for removing Cr VI poisonous in soil or sludge has used substantial amounts of chemical agent, the present invention Lower-cost glucose, white granulated sugar, sucrose or ethanol etc. are only used, the cost of medicament is only flocculence, chemical precipitation method Or the 5~10% of ferrite process.
Embodiment:
Technical solution of the present invention is not limited to act embodiment set forth below, further includes between each embodiment Any reasonable combination.
Embodiment one:Present embodiment using organic matter by poisonous Cr VI be changed into the method for trivalent chromium by Following steps carry out:
To containing Cr6+Waste water in add organic matter, control pH=4~8, react 30~60 minutes, that is, complete;
The organic matter is one or more mixtures in any proportion in glucose, white granulated sugar, sucrose or ethanol.
Present embodiment possesses following beneficial effect:
1st, present embodiment will have virose Cr using biological inhibition method6+Fast transition is Cr3+, Cr6+Transition process Safety and environmental protection, positive effect, the conversion of the quick valence state for realizing heavy metal chromium, the processing of the heavy metal Cr suitable for waste water, Reduce Cr6+The harm brought to environment, and processing procedure does not produce extra sludge or sediment, avoids causing secondary dirt Dye;
2nd, present embodiment method can be by virose Cr6+It is completely reformed into Cr3+, equivalent to the removal for having reached 100% Rate;
3rd, the existing method for removing Cr VI poisonous in waste water has used substantial amounts of chemical agent, and present embodiment is only Used lower-cost glucose, white granulated sugar, sucrose or ethanol etc., the cost of medicament be only flocculence, chemical precipitation method or The 5~10% of ferrite process.
Embodiment two:The present embodiment is different from the first embodiment in that:It is described to containing Cr6+Waste water Middle addition organic matter, controls pH=6, reacts 45 minutes, that is, completes;The organic matter is glucose.Other steps and parameter with Embodiment one is identical.
Embodiment three:The present embodiment is different from the first and the second embodiment in that:Cr in the waste water6+'s Concentration is 1 with the BOD concentration ratios that useless Organic substance in water provides:(2~6).Other steps and parameter and embodiment one or Two is identical.
Embodiment four:Present embodiment is unlike embodiment three:Cr in the waste water6+Concentration It is 1 with the BOD concentration ratios that useless Organic substance in water provides:4.Other steps and parameter are identical with embodiment three.
Embodiment five:Present embodiment using organic matter by poisonous Cr VI be changed into the method for trivalent chromium by Following steps carry out:
By organic matter and contain Cr6+Soil or contain Cr6+Sludge mixing, then add domestic sludge, control pH= 4~8, react 60~120 minutes, that is, complete;
The organic matter is glucose, white granulated sugar, sucrose, ethanol, glucose solution, white sand sugar aqueous solution or sucrose water One or more mixtures in any proportion in solution.
Present embodiment possesses following beneficial effect:
1st, present embodiment will have virose Cr using biological inhibition method6+Fast transition is Cr3+, Cr6+Transition process Safety and environmental protection, positive effect, the conversion of the quick valence state for realizing heavy metal chromium, suitable for the place of soil or the heavy metal Cr of sludge Reason, reduces Cr6+The harm brought to environment, and processing procedure does not produce extra sludge or sediment, avoids causing two Secondary pollution;
2nd, present embodiment method can be by virose Cr6+It is completely reformed into Cr3+, equivalent to the removal for having reached 100% Rate;
3rd, the existing method for removing Cr VI poisonous in soil or sludge has used substantial amounts of chemical agent, this implementation Mode has only used lower-cost glucose, white granulated sugar, sucrose or ethanol etc., and the cost of medicament is only that flocculence, chemistry are heavy The 5~10% of shallow lake method or ferrite process.
Embodiment six:Present embodiment is unlike embodiment five:The quality of the domestic sludge Mass ratio with organic matter is 1:(0.95~1.2).Other steps and parameter are identical with embodiment five.
Embodiment seven:Present embodiment is unlike embodiment five or six:The soil or sludge In the Cr that includes6+Mass content and soil or the ratio of mass content of the organic matter in sludge be 1:(3~7).Other steps It is identical with embodiment five or six with parameter.
Embodiment eight:Present embodiment is unlike embodiment seven:Cr in the soil6+Quality Content is 1 with the BOD mass contents ratio that organic matter in soil provides:6.Other steps and parameter and seven phase of embodiment Together.
Embodiment nine:Present embodiment is unlike embodiment seven:Cr in the sludge6+Quality Content is 1 with the BOD mass contents ratio that organic matter in sludge provides:4.The quality of the domestic sludge and the mass ratio of organic matter For 1:1.Other steps and parameter are identical with embodiment seven.
Embodiment ten:Present embodiment is unlike embodiment seven:Cr in the sludge6+Quality Content is 1 with the BOD mass contents ratio that organic matter in sludge provides:3.Other steps and parameter and seven phase of embodiment Together.
Beneficial effects of the present invention are verified using following embodiments:
Embodiment 1:
Poisonous Cr VI is changed into the method for trivalent chromium by the present embodiment using organic matter, this method according to the following steps into OK:
To containing Cr6+Waste water in add organic matter, control pH=6, react 45 minutes, that is, complete;Cr in the waste water6 +The BOD concentration ratios that provide of concentration and useless Organic substance in water be 1:4;The organic matter is glucose.
Cr in the present embodiment waste water6+Original concentration be 150mg/L, after tested, the present embodiment processing after waste water in Cr6 +Concentration be 0mg/L, illustrate that the present embodiment method can be by virose Cr6+It is completely reformed into Cr3+, equivalent to having reached 100% Removal rate;
Embodiment 2:
Poisonous Cr VI is changed into the method for trivalent chromium by the present embodiment using organic matter, this method according to the following steps into OK:
By organic matter and contain Cr6+Soil mixing, then add domestic sludge, control pH=8, react 120 minutes, i.e., Complete;The Cr included in the soil6+Mass content and soil in organic matter mass content ratio be 1:6;The life The quality of sludge living and the mass ratio of organic matter are 1:1;The organic matter is second alcohol and glucose, the quality of second alcohol and glucose Than for 1:1;
Cr in the present embodiment soil6+Original quality content be 50mg/kg, after tested, the present embodiment processing after soil Middle Cr6+Mass content be 0mg/kg, illustrate that the present embodiment method can be by virose Cr6+It is completely reformed into Cr3+, equivalent to 100% removal rate is reached.
Embodiment 3:
Poisonous Cr VI is changed into the method for trivalent chromium by the present embodiment using organic matter, this method according to the following steps into OK:
By organic matter and contain Cr6+Sludge mixing, then add domestic sludge, control pH=4, react 60 minutes, i.e., Complete;The Cr included in the sludge6+Mass content and sludge in organic matter mass content ratio be 1:3;The life The quality of sludge living and the mass ratio of organic matter are 1:1;The organic matter is glucose.
Cr in the present embodiment sludge6+Original quality content be 60mg/kg, after tested, the present embodiment processing after sludge Middle Cr6+Mass content be 0mg/kg, illustrate that the present embodiment method can be by virose Cr6+It is completely reformed into Cr3+, equivalent to 100% removal rate is reached.

Claims (10)

  1. A kind of 1. method that poisonous Cr VI is changed into trivalent chromium using organic matter, it is characterised in that:This method is by following Step carries out:
    To containing Cr6+Waste water in add organic matter, control pH=4~8, react 30~60 minutes, that is, complete;The organic matter For one or more mixtures in any proportion in glucose, white granulated sugar, sucrose or ethanol.
  2. 2. poisonous Cr VI is changed into the method for trivalent chromium using organic matter according to claim 1, it is characterised in that: It is described to containing Cr6+Waste water in add organic matter, control pH=6, react 45 minutes, that is, complete;The organic matter is grape Sugar.
  3. 3. the method according to claim 1 or 2 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature It is:Cr in the waste water6+The BOD concentration ratios that provide of concentration and useless Organic substance in water be 1:(2~6).
  4. 4. the method according to claim 3 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature are existed In:Cr in the waste water6+The BOD concentration ratios that provide of concentration and useless Organic substance in water be 1:4.
  5. A kind of 5. method that poisonous Cr VI is changed into trivalent chromium using organic matter, it is characterised in that:This method is by following Step carries out:
    By organic matter and contain Cr6+Soil or contain Cr6+Sludge mixing, then add domestic sludge, control pH=4~8, Reaction 60~120 minutes, that is, complete;The organic matter is glucose, white granulated sugar, sucrose, ethanol, glucose solution, white sand One or more mixtures in any proportion in sugar aqueous solution or aqueous sucrose solution.
  6. 6. the method according to claim 5 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature are existed In:The quality of the domestic sludge and the mass ratio of organic matter are 1:(0.95~1.2).
  7. 7. the method that poisonous Cr VI is changed into trivalent chromium using organic matter according to claim 5 or 6, its feature It is:The Cr included in the soil or sludge6+Mass content and soil or the organic matter in sludge mass content ratio For 1:(3~7).
  8. 8. the method according to claim 7 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature are existed In:Cr in the soil6+Mass content and soil in organic matter provide BOD mass contents ratio be 1:6.
  9. 9. the method according to claim 7 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature are existed In:Cr in the sludge6+Mass content and sludge in organic matter provide BOD mass contents ratio be 1:4.
  10. 10. the method according to claim 7 that poisonous Cr VI is changed into trivalent chromium using organic matter, its feature are existed In:Cr in the sludge6+Mass content and sludge in organic matter provide BOD mass contents ratio be 1:3.
CN201711340997.5A 2017-12-14 2017-12-14 A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter Pending CN108017136A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437384A (en) * 2018-11-28 2019-03-08 大连理工大学 Copper ion accelerates fructose-K2HPO4The method of product processing waste water containing chrome

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Publication number Priority date Publication date Assignee Title
CN101519241B (en) * 2009-04-07 2010-12-08 同济大学 Method for deoxidizing hexavalent chromium in wastewater by using sludge
WO2015145051A1 (en) * 2014-03-28 2015-10-01 Ms Developpement Et Participations Method for treating chromium present in effluents, and corresponding equipment
CN105255782A (en) * 2015-11-16 2016-01-20 四川省兰月科技有限公司 Cellulosimicrobium cellulans with reducing capacity on hexavalent chromium and application
CN106277420A (en) * 2015-06-03 2017-01-04 中国科学院过程工程研究所 A kind of dechromium method of organic reducing Cr VI alkaline waste liquor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519241B (en) * 2009-04-07 2010-12-08 同济大学 Method for deoxidizing hexavalent chromium in wastewater by using sludge
WO2015145051A1 (en) * 2014-03-28 2015-10-01 Ms Developpement Et Participations Method for treating chromium present in effluents, and corresponding equipment
CN106277420A (en) * 2015-06-03 2017-01-04 中国科学院过程工程研究所 A kind of dechromium method of organic reducing Cr VI alkaline waste liquor
CN105255782A (en) * 2015-11-16 2016-01-20 四川省兰月科技有限公司 Cellulosimicrobium cellulans with reducing capacity on hexavalent chromium and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437384A (en) * 2018-11-28 2019-03-08 大连理工大学 Copper ion accelerates fructose-K2HPO4The method of product processing waste water containing chrome

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