CN102633618A - Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof - Google Patents
Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof Download PDFInfo
- Publication number
- CN102633618A CN102633618A CN2012101006843A CN201210100684A CN102633618A CN 102633618 A CN102633618 A CN 102633618A CN 2012101006843 A CN2012101006843 A CN 2012101006843A CN 201210100684 A CN201210100684 A CN 201210100684A CN 102633618 A CN102633618 A CN 102633618A
- Authority
- CN
- China
- Prior art keywords
- acid titanium
- alcohol acid
- titanium complex
- soil
- halogenated organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses hydroxy acid titanium complexes promoting the detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as a preparation method and an application of the hydroxy acid titanium complexes. The preparation method of the hydroxy acid titanium complexes comprises the following steps of: mixing a titanium trichloride water solution with a hydroxy acid ligand water solution according to the molar ratio of titanium trichloride to hydroxy acid ligand being 8:1-1:10 under an anaerobic condition, adjusting pH of a reaction liquid to be 8.0-8.8, reacting for 1-2hours in a stirring way, readjusting pH value of the reaction liquid to be 9.2-9.8, and reacting for 1-2.5hours in a stirring way, so that a hydroxy acid titanium complexes-containing solution can be obtained. The hydroxy acid titanium complexes disclosed by the invention are good in stability under the anaerobic condition, and durable in reducibility, under the mediation of vitamin, the hydroxy acid titanium complexes are very high in reduction activity, so that the reductive transformation and the degradation of the halogenated organic pollutant in the soil can be effectively promoted, and the reductive transformation capability of the halogenated organic pollutants such as pentachlorophenol, polychlorinated biphenyl, propachlor, 2, 4, 6-tribromophenol and the like in the soil are all more than 80%, thus being particularly suitable for the treatment of different halogenated organic pollutants with higher concentrations by means of reductive dehalogenation.
Description
Technical field:
The invention belongs to soil pollution and repair the field, be specifically related to one type of alcohol acid titanium complex that promotes halogenated organic matters contaminated soil dehalogenation and detoxification.
Background technology:
Halogenated organic matters is one type of important pollutent in the soil.Chlorinatedorganic mainly comprises in the soil: chlorinated aliphatic hydrocarbon, chlorinated benzene, brominated flame-retardant, acetamide-group herbicides etc.These pollutents are mainly derived from industrial pollution source, agricultural chemicals, chemical fertilizer, solid waste (electronic waste etc.) and agricultural use etc.; And extended residual is in soil; Through the geochemical process polluted underground water; Pollute whole soil system through the environmental geochemistry process, and further endanger the health of animals and human beings class through food chain.Halogenated organic matters toxicity largely is the halogen element in the molecular structure.And there are some researches show that it is the surface reaction process that extensively exists in the soil that dehalogenation transforms, also be the main process of halogenated organic matters toxicide simultaneously.The dehalogenation and detoxification of studying halogenated organic matters in these soil is the focus of studying both at home and abroad always.At present, having caused attention widely for the conversion of halogenated organic matters in soil and processing, comprised soil activation mineral interfaces such as soil red stone, manganese oxide, is the important media that the halogenated organic matters dechlorination transforms.
Except that ground surface soil, soil is in anoxic or oxygen-free environment basically, and therefore, for the vattability organic pollutant, it is that its most basic while in the middle of soil also is most important conversion degradation pathway that the reduction under the anaerobic condition transforms detoxifcation.The vital role that the moity of soil itself (like soil activation mineral etc.) may produce for the organic degradation-detoxification process of vattability wherein; There is the soil chemistry investigator to attempt utilizing the primary activity element in the soil; Invention can promote the reaction reagent that the organism dechlorination transforms in the soil, has obtained certain effect.Account for the 9th and the tenth respectively like ferro element and the abundance of manganese element in the earth's crust; Be the occurring in nature minority but belong to common valence variation element; Has very high reducing activity; They are present in soil and the settling with various forms and valence state, have very high redox active and can participate in various chemical reactions, thereby playing an important role aspect control surface water and the soil pollution.High reactivity based on iron and manganese; Chinese patent ZL200710028313 Li Fangbai etc. makes full use of various ligand ions can promote the active iron species of high reductibility and the characteristic that the manganese species produce; A series of iron and manganese complex materials that can promote many halogenated organic matters dehalogenation and detoxification in the soil have been synthesized; Be applied to the improvement that agricultural land soil, electronic waste pollute contaminated sites such as disposal field, can quicken pollutent such as many halogenated organic matters in the soil dehalogenation and detoxification, improve soil self purification activity, promote the improvement of electronic waste contaminated site.
Titanium also is a kind of active element in the middle of the soil, and titaniferous ore has higher activity in soil.Titanium oxide has received very big concern in the time in 20 years nearly in the past as a kind of highly active photocatalyst.Very many RPs with patent report the photocatalyst of research and utilization titanium oxide as water treatment and topsoil organic contamination reparation; And utilize different rare earth metals that titanium oxide is mixed; Improve the titanium oxide energy gap; The wavelength that enlarges light source capable of using has improved application possibility and the range of application of titanium oxide as photocatalyst to visible-range.Titanous chloride is one of muriate of titanium, and chemical formula is TiCl
3Titanous chloride is one of common titanium compound, main catalyzer as olefinic polyreaction in industry.Titanous chloride generally makes through the reduction titanium tetrachloride, and reductive agent can be hydrogen, titanium simple substance or other metals.Titanous chloride also can be through reducing Ti in the solution
IVObtain.Rare gas element exists down, and its aqueous solution state is more stable.Owing to be layer-lattice structure in the titanous chloride structure, the cl ions in the structure is cube tightly packed, and each titanium atom has 1 d electronics, and most of variants all are paramagnetic, and Ti-Ti is apart from doing
Therefore, TiCl
3Can generate a lot of title complexs.If any report, when titanous chloride and THF reflux, can generate nattier blue crystal adducts TiCl
3(THF)
3:
TiCl
3+3C
4H
8O→TiCl
3(OC
4H
8)
3
Generate serpentinous neutral products with the n n dimetylaniline coordination:
TiCl
3+3Me
2NH→TiCl
3(NHMe
2)
3+CH
3Cl
TiCl
3Generate the tri acetylacetonato title complex with the methyl ethyl diketone reaction:
TiCl
3+3NH
4(acac)→Ti(acac)
3+3NH
4Cl
The title complex that produces is the octahedral build mostly, and ligating atom is O-or N-, and present application mainly concentrates on the linking agent as cellulosefilm in the polyethylene catalysts.
Except that containing carboxyl, also contain the compound of other functional groups in the molecule, be called carboxylic acid, be called substituted carboxylic acid again with complex function group.Alcohol acid is exactly a kind of of substituted carboxylic acid, has not only contained hydroxyl in the molecule but also has contained the Complex functional group compounds of carboxyl.Alcohol acid extensively is formed in the bodies of aminal and plant, and has plenty of the material that carries out vital movement in the organism, has plenty of the raw material of synthetic drugs, the seasonings as food that has.Contain hydroxyl and carboxyl in the alcohol acid molecule, have the general aspects of hydroxyl and carboxyl.Therefore, alcohol acid combines with metals ion in solution, is easy to form alcohol acid-metal ion match, and title complex demonstrates the high characteristics of stable in properties reactive behavior.
Summary of the invention:
The objective of the invention is to lack and the low deficiency of remediation efficiency to soil halo organic pollutant reduction renovation agent in the prior art, provide one type under anaerobic good stability, can keep alcohol acid titanium complex of persistent reducing activity, promotion halogenated organic matters contaminated soil dehalogenation and detoxification that remediation efficiency is high and preparation method thereof.
The alcohol acid titanium complex of promotion halogenated organic matters contaminated soil dehalogenation and detoxification of the present invention is through the method preparation, and this method may further comprise the steps:
Is that 8: 1～1: 10 ratio is mixed under oxygen free condition with titanium trichloride aqueous solution and the alcohol acid part aqueous solution according to titanous chloride and alcohol acid part mol ratio; Under oxygen free condition; Conditioned reaction liquid pH to 8.0～8.8, stirring reaction 1～2h, and then conditioned reaction liquid pH value to 9.2～9.8; Stirring reaction 1～2.5h, and obtain the solution of hydroxyl-containing acid titanium complex.
Described alcohol acid part is preferably a kind of in oxalic acid, oxysuccinic acid, tartrate or the Hydrocerol A part or several, and its source preferably is respectively sodium oxalate, sodium malate, sodium tartrate and Trisodium Citrate.
Described adjusting pH value preferably under oxygen free condition, is used solid phase Na
2CO
3Conditioned reaction liquid pH value to 8.0～8.8, stirring reaction 1～2h, and then use saturated Na
2CO
3Solution conditioned reaction liquid pH value to 9.2～9.8, stirring reaction 1～2.5h.
Second purpose of the present invention provides the application of alcohol acid titanium complex in promoting the halogenated organic matters reductive dehalogenation.
The preferably application of alcohol acid titanium complex associating VITAMINs in promoting the halogenated organic matters reductive dehalogenation.
Described Vitamin U is elected vitamins B as
12With in the vitamins C one or both.
Described alcohol acid titanium complex associating vitamins B
12, alcohol acid titanium complex and vitamins B
12United use in 1: 3 in molar ratio～3: 1.
Described alcohol acid titanium complex associating vitamins C, alcohol acid titanium complex and vitamins C were united use in 1: 4.5 in molar ratio～5: 1.
Concrete method of use is: at first in the target soil that halogenated organic matters pollutes, add a certain amount of alcohol acid titanium complex renovation agent (aqueous solution of alcohol acid titanium complex), leave standstill 10～30min after, add vitamin solution, like vitamins B
12Or vitamin c solution, the alcohol acid titanium complex of adding is following with the mol ratio of different VITAMINss: alcohol acid titanium complex/vitamins B
12=1: 3～3: 1; Alcohol acid titanium complex/vitamins C=1: 4.5～5: 1 adds water to the whole submergences of soil to processing soil then.
With the reparation reagent and the compared with techniques of existing soil, the present invention has the following advantages:
1. the present invention makes full use of the characteristic that alcohol acid can promote the active titanium generation of high reductibility; Synthesized a series of alcohol acid titanium complex; This alcohol acid titanium complex is good stability under anaerobic; Can keep persistent reductibility, the halogenated organic matters contaminated soil dehalogenation and detoxification that is beneficial under the anoxia condition of non-top layer is administered.
2. vitamins B
12With the reducing property of VITAMINs such as vitamins C as electron mediator mediation activation alcohol acid titanium complex; Make the alcohol acid titanium complex have very high reducing activity, under anaerobic or the anoxia condition, can promote the reduction of halo organic pollutant in the soil to transform and degraded effectively; Through the experiment proof; Its to the reduction conversion capability of halo organic pollutants such as Woodtreat A, polychlorobiphenyl, propachlor, bromol in the soil all above 80%; The reductive dehalogenation that is particularly suitable for the different organo-chlorine pollutants of higher concentration is administered, and remediation efficiency is high.
3. in use, alcohol acid titanium complex renovation agent of the present invention is liquid, and VITAMINs also is liquid; And there is not any toxicity; Be environmental friendliness reagent, can in the terrain soil remediation, be injected into deep soil, to repair darker underground halo organic pollutant contaminated soil as renovation agent.
4. titanium involved in the present invention, hydroxy organic acid and VITAMINs are environment-friendly material, and also are the soil constituent that itself has in the middle of the healthy soil, therefore, in use can not cause any secondary pollution to target soil.
5. the preparation method of alcohol acid titanium complex of the present invention carries out under normal temperature and normal pressure, mild condition, and technology is simple, is convenient to operation, thereby is easy to carry out large-scale production.
Therefore, the present invention can be applicable to quicken the dehalogenation and detoxification of pollutents such as halogenated organic matters such as chlorine in the soil, promotes the improvement of useless admittedly place soil organic pollutants such as electronic waste contaminated site; Simultaneously can make full use of and bring into play the natural self-purification capacity of soil; Regulate through exogenous material; Improve soil processing power to environmental pollutants; Improvement and guarantee ecological security to promoting the electronic waste contaminated site have important environment, society and economic implications, have very high application prospect.
Embodiment:
Following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1: the preparation of Hydrocerol A titanium complex renovation agent
The titanium trichloride aqueous solution of present embodiment is the titanous chloride dilute hydrochloric acid solution of mass concentration 15%, and Citrate trianion is the trisodium citrate (C of purity＞99%
6H
5Na
3O
72H
2O) solid state chemistry reagent.
The preparation method of the Hydrocerol A titanium complex renovation agent of present embodiment comprises the steps:
(1) trisodium citrate is configured to the aqueous solution of 0.8M, in the aqueous solution, charges into nitrogen, continue 30min, sealing is preserved subsequent use as storing solution then;
(2) in many mouthfuls of flasks, add 400mL Titanium Trichloride Solution, inflated with nitrogen 20min;
(3) in many mouthfuls of flasks, add 65mL Trisodium Citrate storing solution again, continue nitrogen filled protection, the mol ratio of titanous chloride and Trisodium Citrate is in the reaction solution: 8: 1;
(4) in the reaction solution of many mouthfuls of flasks, continue trace and add solid state N a
2CO
3, and the pH value of The real time measure reaction solution is when the pH value stops to add to 8.0 the time;
(5) add stirrer, many mouthfuls of flasks continue stirring reaction 1h on whisking appliance, in whipping process, continue to feed nitrogen protection, are stabilized in 8.0 until reacting liquid pH value;
(6) the saturated Na of configuration high density
2CO
3Solution drips Na
2CO
3Solution is gone in the reaction solution of many mouthfuls of flasks, continues in the dropping process to stir and logical nitrogen, is stabilized in 9.2 until reacting liquid pH value, continuously stirring reaction 1h under protection of nitrogen gas;
(7) and then add the dilution of 200mL oxygen-free water, continue to stir 0.5h and mix, obtain Hydrocerol A titanium complex renovation agent, airtight preservation is subsequent use.
Embodiment 2: the preparation of titanous oxalate title complex, oxysuccinic acid titanium complex and tartrate titanium complex renovation agent
The titanium trichloride aqueous solution of present embodiment is the titanous chloride dilute hydrochloric acid solution of mass concentration 15%, and hydroxy-acid salt is respectively sodium oxalate (Na
2C
2O
4), sodium malate (C
4H
4Na
2O
5), sodium tartrate (C
4H
4Na
2O
6), purity is all＞99%.
The preparation method of the titanous oxalate title complex reagent of present embodiment comprises the steps:
(1) sodium oxalate is configured to the aqueous solution of 0.8M, in the aqueous solution, charges into nitrogen, continue 20min, sealing is preserved subsequent use as storing solution then;
(2) in many mouthfuls of flasks, add 25mL Titanium Trichloride Solution, inflated with nitrogen 20min;
(3) in many mouthfuls of flasks, add 325mL sodium oxalate storing solution, continue nitrogen filled protection, the mol ratio of titanous chloride and sodium oxalate is in the reaction solution: 1: 10;
(4) in the reaction solution of many mouthfuls of flasks, continue trace and add solid state N a
2CO
3, and the pH value of The real time measure reaction solution is when the pH value stops to add to 8.8 the time;
(5) add stirrer, many mouthfuls of flasks continue stirring reaction 2h on whisking appliance, in whipping process, continue to feed nitrogen protection, are stabilized in 8.8 until reacting liquid pH value;
(6) the saturated Na of configuration high density
2CO
3Solution drips Na
2CO
3Solution is gone in the reaction solution of many mouthfuls of flasks, continues in the dropping process to stir and logical nitrogen, is stabilized in 9.8 until reacting liquid pH value, continuously stirring reaction 2.5h under protection of nitrogen gas;
(7) and then add the dilution of 400mL oxygen-free water, continue to stir 1.5h and mix, obtain titanous oxalate title complex renovation agent, airtight preservation is subsequent use.
Sodium malate (C
4H
4Na
2O
5) and sodium tartrate (C
4H
4Na
2O
6) handle equally according to the method described above, obtaining oxysuccinic acid titanium complex and tartrate titanium complex renovation agent, airtight preservation is subsequent use.
Embodiment 3: mix the preparation of alcohol acid titanium complex reagent
The purity of various hydroxy-acid salt solution and Titanium Trichloride Solution reagent and compound method such as embodiment 1 and 2.
(1) Trisodium Citrate, sodium oxalate, sodium malate and sodium tartrate are configured to the aqueous solution of 0.8M respectively, in the aqueous solution, charge into nitrogen, continue 20min, sealing is preserved subsequent use as storing solution then;
(2) in many mouthfuls of flasks, add 25mL Titanium Trichloride Solution, inflated with nitrogen 20min;
(3) in many mouthfuls of flasks, add Trisodium Citrate storing solution 20mL, sodium oxalate storing solution 15mL, sodium malate storing solution 15mL and sodium tartrate storing solution 15mL, titanous chloride is 1: 2 with the mol ratio of total alcohol acid group in the reaction solution;
(4) in the reaction solution of many mouthfuls of flasks, continue trace and add solid state N a
2CO
3, and the pH value of The real time measure reaction solution is when the pH value stops to add to 8.5 the time;
(5) add stirrer, many mouthfuls of flasks continue stirring reaction 1h on whisking appliance, in whipping process, continue to feed nitrogen protection, are stabilized in 8.5 until reacting liquid pH value;
(6) the saturated Na of configuration high density
2CO
3Solution drips Na
2CO
3Solution is gone in the reaction solution of many mouthfuls of flasks, continues in the dropping process to stir and logical nitrogen, is stabilized in 9.5 until reacting liquid pH value, continuously stirring reaction 1h under protection of nitrogen gas;
(7) and then add the dilution of 200mL oxygen-free water, continue to stir 0.5h and mix, obtain mixing alcohol acid titanium complex renovation agent, airtight preservation is subsequent use.
Embodiment 4: the alcohol acid titanium complex in homogeneous system to the organo-chlorine pollutant dehalogenation and detoxification
Designed following experiment and studied the application of alcohol acid titanium in the halo organic pollutant governance process in the homogeneous system: reaction solution (propachlor solution) is with 0.1m
3The speed inflated with nitrogen deoxygenation of/min continues balance 2h and keeps anaerobic environment.Entire reaction adopts cillin bottle (20ml) batch processing experiment reaction system.Use transfer pipet to shift synthetic concentration at the anaerobism worktable and go in the cillin bottle, and draw the 5mL vitamins B as the alcohol acid titanium complex renovation agent of 0.8M
12Solution (1M) is gone into (vitamins B in the cillin bottle
12Be respectively with titanous oxalate title complex, Hydrocerol A titanium complex, oxysuccinic acid titanium complex, tartrate titanium complex, the mol ratio of mixing the alcohol acid titanium complex respectively: 3: 1,2: 1,1: 1,1: 2,1: 3), cover serum cap, whole process is accomplished in 15min; And the lasting nitrogen that in cillin bottle, fills; Add aluminium lid sealing, put into 25 ± 1 ℃ of constant incubators, leave standstill, timing; The reaction beginning, the manually light rolling reaction of every 1h cillin bottle.The bottle number is confirmed according to sampling number.
During mensuration, get 1 bottle at random, reaction solution is shaken up, pick aluminium lid then, open plug.Centrifugal (6500rpm 10-20min) separates, and gets supernatant, the dehalogenation rate of HPLC analytical reaction, and five kinds of alcohol acid titanium complexes all meet apparent first order kinetics to the degradation process of propachlor, according to its kinetic constant of first order kinetics Model Calculation (seeing table 1).
Table 1: the dechlorination of organochlorine contamination thing in the homogeneous system
Embodiment 5: the application of alcohol acid titanium complex in the halo organic pollutant governance process in the soil system
Gather Guangdong Province's Qingyuan City red soil sample; Woodtreat A, polychlorobiphenyl, propachlor, 2 with 1.0mM concentration; 4; 6-bromophenisic acid solution mixes simultaneously, after the state of nature air dried, adopts the dehalogenation transformation efficiency of earth pillar experimental verification alcohol acid titanium complex of the present invention to four kinds of halo organic pollutants.
Test following: the high 1m of earth pillar, diameter 20cm with the concrete parameter of earth pillar reactor drum; Layering 3-5 layer combination makes up, every layer of 20cm or 30cm, every layer of loading and unloading easily; Every layer of post jamb is provided with fetch earth earth sample well and filtrate collection hole; Can monitor to pollute and repair the control effect, easy and simple to handle, can amplify according to experiment and the combination of pollution remediation technology flexible design.
In the reaction system, with alcohol acid titanium complex renovation agent (0.01～0.2M) with vitamin b6 usp B
12, soil (is respectively enrichment Woodtreat A, polychlorobiphenyl, propachlor, 2; 4; The soil of 6-bromophenisic acid) be filled in the earth pillar reactor drum according to mol ratio 1: 1: 5～10 blending methods, use hydrochloric acid to regulate earth pillar system pH and be subacidity, continue to charge into slowly nitrogen (0.05m at earth pillar upper opening place
3/ min), regular collection soil sample analysis.Under the simulated rainfall conditions (0.02mm/min), in the earth sample that fetches earth, collect filtrate analysis.The starting point concentration value of four kinds of halo organic pollutants then during natural air drying, directly adopts acetone extract in the soil after mixing, concentrates the back and adopts HPLC to analyze its concentration.The initial concentration that records Woodtreat A, polychlorobiphenyl, propachlor, bromol is respectively 15.2mg/kg, 10.7mg/kg, 8.6mg/kg, 7.9mg/kg.The earth pillar of filling polluted soil has the ability of the very high many halogenated organic matters of degraded.The reduction dechlorination of reaction pair Woodtreat A, polychlorobiphenyl, propachlor, bromol all meets apparent first order reaction kinetic.The dechlorination rate of resulting four kinds of halo organic pollutants and first order kinetics constant k value result see table 2.
Table 2: the dehalogenation rate and the first order kinetics constant value of four kinds of halo organic pollutants in the earth pillar experiment
This shows; Titanous oxalate title complex, Hydrocerol A titanium complex, oxysuccinic acid titanium complex, tartrate titanium complex and mixing alcohol acid titanium complex are to Woodtreat A, polychlorobiphenyl, propachlor, 2; 4; The reduction conversion capability of halo organic pollutants such as 6-bromophenisic acid is all above 80%, and the reductive dehalogenation that is particularly suitable for the different organo-chlorine pollutants of higher concentration is administered, and remediation efficiency is high.
Embodiment 6: alcohol acid titanium complex renovation agent transforms the reductive dehalogenation of halo organic pollutant under the different soils condition
The present invention is based on the following soil anaerobic environment in top layer, in the soil remediation process, there is certain difference in actual different soils condition for repairing reagent dosage and use meeting.Therefore can obviously influence the dechlorination detoxification processes and the effect of soil halo organic pollutant based on the adjusting of edaphic condition, and, add the external source reductive agent or artificially build the dehalogenation degradation process that some halo organic pollutant more can induced or quicken to anaerobic condition.
Present embodiment has designed following experiment the method for use of alcohol acid titanium complex of the present invention in reagent soil remediation process has been described: will use weedicide propachlor and 2 in a large number; 4; The paddy rice sample plot of 6-bromophenisic acid, a part changes the nonirrigated farmland into, and a part keeps original paddy field state.Simultaneously application concentration is the different alcohol acid titanium complex solution of 0.8M and vitamin c solution (volume ratio 1: 0.16, mol ratio 5: 1) that concentration is 1M.The soil at the regular following 15cm of acquisition test surface layer place with propachlor in the acetone extract soil and metolachlor, carries out HPLC to extraction liquid then and analyzes weekly, and the result finds propachlor and 2 in the sample plot of paddy field; 4,6-bromophenisic acid concentration is starkly lower than propachlor and 2,4 in the sample plot of nonirrigated farmland; The concentration of 6-bromophenisic acid concentration, and propachlor and 2,4 in the paddy field; The degradation rate of 6-bromophenisic acid is obviously tested the degradation rate of Tanaka's propachlor and bromol faster than the nonirrigated farmland.The fall off rate of propachlor and bromol is propachlor and bromol fall off rate 3.6～4.7 times and 4.1～4.9 times in the nonirrigated farmland in the paddy field soil.The reduction potential of sampling analysis experiment field soil, the reduction potential in the paddy field soil progressively is lowered into strong reduced state (low potential) by the strong state of oxidation (noble potential); The reduction potential rate of change of reduction potential rate of change in the dryland soil in the paddy field soil.Above experimental result explanation alcohol acid titanium complex is under waterflooding, anaerobic condition; In the environment of low potential (strong reducing property), has very high chemically reactive; Since the active enhancing of high reductibility alcohol acid titanium complex, propachlor and 2,4; The reductive dehalogenation conversion process of 6-bromophenisic acid is obviously accelerated, and has quickened to receive the self-purification capacity of halo organic pollutant contaminated soil greatly.The dehalogenation rate and the first order kinetics constant value of propachlor and bromol are seen table 3.
Table 3: the dechlorination rate and the first order kinetics constant value of experiment field soil poisoning grass amine and bromol
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being made, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one type of preparation method who promotes the alcohol acid titanium complex of halogenated organic matters contaminated soil dehalogenation and detoxification; It is characterized in that; May further comprise the steps: is that 8: 1～1: 10 ratio is mixed under oxygen free condition with titanium trichloride aqueous solution and the alcohol acid part aqueous solution according to titanous chloride and alcohol acid part mol ratio, under oxygen free condition, and conditioned reaction liquid pH to 8.0～8.8; Stirring reaction 1～2h; And then conditioned reaction liquid pH value to 9.2～9.8, stirring reaction 1～2.5h, and obtain the solution of hydroxyl-containing acid titanium complex.
2. preparation method according to claim 1 is characterized in that, described alcohol acid part is a kind of in oxalic acid, oxysuccinic acid, tartrate or the Hydrocerol A part or several.
3. preparation method according to claim 2 is characterized in that, the source of described oxalic acid, oxysuccinic acid, tartrate or Hydrocerol A part is respectively sodium oxalate, sodium malate, sodium tartrate and Trisodium Citrate.
4. preparation method according to claim 1 is characterized in that, described adjusting pH value is under oxygen free condition, uses solid phase Na
2CO
3Conditioned reaction liquid pH value to 8.0～8.8, stirring reaction 1～2h, and then use saturated Na
2CO
3Solution conditioned reaction liquid pH value to 9.2～9.8, stirring reaction 1～2.5h.
5. the alcohol acid titanium complex for preparing of the preparation method of the alcohol acid titanium complex of one type of promotion halogenated organic matters contaminated soil dehalogenation and detoxification according to claim 1.
6. the application of the described alcohol acid titanium complex of claim 5 in promoting the halogenated organic matters reductive dehalogenation.
7. application according to claim 6 is characterized in that, described alcohol acid titanium complex is the application of associating VITAMINs in promoting the halogenated organic matters reductive dehalogenation.
8. application according to claim 7 is characterized in that, described VITAMINs is vitamins B
12With in the vitamins C one or both.
9. application according to claim 8 is characterized in that, described alcohol acid titanium complex associating vitamins B
12, alcohol acid titanium complex and vitamins B
12United use in 1: 3 in molar ratio～3: 1.
10. application according to claim 8 is characterized in that, described alcohol acid titanium complex associating vitamins C, and alcohol acid titanium complex and vitamins C were united use in 1: 4.5 in molar ratio～5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101006843A CN102633618A (en) | 2012-04-06 | 2012-04-06 | Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101006843A CN102633618A (en) | 2012-04-06 | 2012-04-06 | Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102633618A true CN102633618A (en) | 2012-08-15 |
Family
ID=46618219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101006843A Pending CN102633618A (en) | 2012-04-06 | 2012-04-06 | Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633618A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026062A (en) * | 2013-03-08 | 2015-11-04 | 朗恩-赛尔斯公司 | Use of acidogenic leachate, method and plant for soil washing |
| CN110551505A (en) * | 2019-08-02 | 2019-12-10 | 湖南恒凯环保科技投资有限公司 | Combined reagent and method for repairing pentachlorophenol polluted soil |
| CN111220766A (en) * | 2020-01-21 | 2020-06-02 | 广东省生态环境技术研究所 | Method for obtaining variable-charge soil charge zero point |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645374A (en) * | 1995-11-27 | 1997-07-08 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of The Environment | Method for dehalogenating contaminated water and soil |
| CN101489941A (en) * | 2005-11-10 | 2009-07-22 | 耶达研究及发展有限公司 | Catalytically treating water contaminated with halogenated organic compounds |
-
2012
- 2012-04-06 CN CN2012101006843A patent/CN102633618A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645374A (en) * | 1995-11-27 | 1997-07-08 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of The Environment | Method for dehalogenating contaminated water and soil |
| CN101489941A (en) * | 2005-11-10 | 2009-07-22 | 耶达研究及发展有限公司 | Catalytically treating water contaminated with halogenated organic compounds |
Non-Patent Citations (7)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026062A (en) * | 2013-03-08 | 2015-11-04 | 朗恩-赛尔斯公司 | Use of acidogenic leachate, method and plant for soil washing |
| CN110551505A (en) * | 2019-08-02 | 2019-12-10 | 湖南恒凯环保科技投资有限公司 | Combined reagent and method for repairing pentachlorophenol polluted soil |
| CN110551505B (en) * | 2019-08-02 | 2020-10-02 | 湖南恒凯环保科技投资有限公司 | Combined reagent and method for repairing pentachlorophenol polluted soil |
| CN111220766A (en) * | 2020-01-21 | 2020-06-02 | 广东省生态环境技术研究所 | Method for obtaining variable-charge soil charge zero point |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kappler et al. | An evolving view on biogeochemical cycling of iron | |
| Daugherty et al. | Complexation and redox buffering of iron (II) by dissolved organic matter | |
| Dong et al. | Remediation of vanadium-contaminated soils by the combination of natural clay mineral and humic acid | |
| Shi et al. | Progress in the remediation of hazardous heavy metal-polluted soils by natural zeolite | |
| Boyd et al. | The biogeochemical cycle of iron in the ocean | |
| Yokoyama et al. | Differences in the immobilization of arsenite and arsenate by calcite | |
| Kraemer et al. | Siderophores and the dissolution of iron-bearing minerals in marine systems | |
| Jung et al. | Redox cycling driven transformation of layered manganese oxides to tunnel structures | |
| CN107459992A (en) | The preparation method and modification biological charcoal of the sulfhydryl modified charcoal of sulfenyl | |
| Zhu et al. | Effects of dissolved organic matter on adsorbed Fe (II) reactivity for the reduction of 2-nitrophenol in TiO2 suspensions | |
| Chien et al. | Reactions of compost-derived humic substances with lead, copper, cadmium, and zinc | |
| Qu et al. | Surface complexation modeling of Cu (II) sorption to montmorillonite–bacteria composites | |
| Xu et al. | Metal–organic framework-5 as a novel phosphorescent probe for the highly selective and sensitive detection of Pb (II) in mussels | |
| CN108912341B (en) | Host-guest lead coordination polymer, preparation method and application thereof in cation detection | |
| CN102633618A (en) | Hydroxy acid titanium complexes promoting detoxification of halogenated organic matter-polluted soil by means of dehalogenation, as well as preparation and application thereof | |
| Wang et al. | Oxidation of Mn (III) species by Pb (IV) oxide as a surrogate oxidant in aquatic systems | |
| Chubar et al. | Sorption and precipitation of Mn2+ by viable and autoclaved Shewanella putrefaciens: Effect of contact time | |
| Balland-Bolou-Bi et al. | Increased Mg release rates and related Mg isotopic signatures during bacteria-phlogopite interactions | |
| Yang et al. | Significantly enhanced P release from vivianite as a fertilizer in rhizospheric soil: Effects of citrate | |
| CN107983294B (en) | Polysaccharide modified ferro-manganese bimetallic material and preparation method and application thereof | |
| Sun et al. | High arsenic levels in sediments, Jianghan Plain, central China: Vertical distribution and characteristics of arsenic species, dissolved organic matter, and microbial community | |
| Yi et al. | Influencing factors and environmental effects of interactions between goethite and organic matter: A critical review | |
| Liang et al. | Tracing the synergistic migration of biochar and heavy metals based on 13C isotope signature technique: Effect of ionic strength and flow rate | |
| CN104892598A (en) | A 1,10-fenanthrolin derivative, a preparing method thereof and applications of the derivative | |
| Gusiatin et al. | Influence of soil aging and stabilization with compost on Zn and Cu fractionation, stability, and mobility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |