CN1238074C - Decomposition treatment process for dioxine - Google Patents
Decomposition treatment process for dioxine Download PDFInfo
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- CN1238074C CN1238074C CNB01123184XA CN01123184A CN1238074C CN 1238074 C CN1238074 C CN 1238074C CN B01123184X A CNB01123184X A CN B01123184XA CN 01123184 A CN01123184 A CN 01123184A CN 1238074 C CN1238074 C CN 1238074C
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- Environmental & Geological Engineering (AREA)
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Abstract
The present invention provides a method for simply performing the decomposition of dioxins contained in fly ash, soil or the like without forming toxic byproducts. The decomposition method decomposes or dechlrinates dioxins in an object to be treated by bringing dioxins contained in the object to be treated to a Grignard reagent state, its characteristic is based on that it consists of a dehydration process for removing moisture of the treated object containing dioxins, a mixing process for mixing a magnesium powder with the object to be treated obtained in the dehydration process, a heating process for heating the object to be treated at least at one point of time selected from points of time before, after and during the mixing process, and an acceleration liquid adding process for adding an acceleration liquid, which generates reducing reaction, to dioxins held to the Grignard reagent state in the object to be treated obtained after the mixing process and the heating process.
Description
The present invention relates to flying dust, burn De dioxin in ash, mud or greasy filth the like waste and soil etc. (below be called " the object being treated ") solid, do not generating toxic byproduct, needn't do with external heat means or burning etc. under the situation of high temperature heating, carry out the method for easy resolution process by effective decomposition or dechlorination, the present invention also preferably relates to and prevents the decomposing process of heavy metal by stripping De dioxin in the processed solid after handling.
As everyone knows, dioxin can cause skin and internal organ disease, and teratogenesis and carcinogenicity are arranged, and is to remove this not precedented extremely toxic substance.Narrow sense De bioxin 2,3,7 particularly, 8-tetrachloro dibenzo Dui bioxin, one of the highest material of the human obtained toxicity of being known as.In addition, other dioxin also is harmful to human body, and wherein, toxicity that it is generally acknowledged Polychlorinated biphenyls (PCB) also is the problem of need research, but the PCB of coplane particularly has the extremely strong planar structure of toxicity in PCB.
In recent years, people have carried out all censuring to the pollution problem that this hypertoxic De dioxin causes.Particularly find to have the situation that generates bioxin because of burning away the refuse, and then constituted such problem, promptly, because the operating condition of waste incineration field, because of burning away the refuse the generation dioxin, generate the De dioxin and sneak into the flying dust of discharging by the waste incineration field, or in the chimney exhaust of waste incineration field the Han dioxin, problems such as burning a peripheral soil has taken place to pollute.
In addition, in previously used agricultural chemicals such as herbicide, contain dioxin as impurity, such situation is arranged: because of using this agricultural chemicals, also residual up to now have a Shou dioxin contaminated soil.
Dioxin is mixed in the above-mentioned discarded object, and problems such as further contaminated soil and river take place.
In addition, after handling with method in the past, social concerns such as environment take place to destroy to outside in harmful heavy metal strippings such as cadmium in the residual solid and lead.
In view of such actual conditions, resolution process technology as absorption, sorption De dioxin in processed has proposed following method: 1. fusion mode, 2. high temperature incineration mode, 3. gas phase hydrogen reduction mode, 4. dechlorination mode, 5. supercritical water oxidation is olation, 6. sodium metal dispersion mode are heated in reduction, 7. photochemistry is olation, 8. dioxin is blended in alkaline ethylene glycol or the alkaline alcohol, is heated to 150 ℃ and kept 90 minutes, the method that the Shi dioxin decomposes etc.
These methods are except that 6. and 7., all must heating, and decompose and need the time.But 6. dangerous, 7. except because of light can not by solid make efficient low, also have problems such as device and operating cost height.
As other resolution process technology, open in the clear 57-52900 communique the spy, following method is disclosed: make contain halogen and/or phosphorus particularly be subjected to alpha-contamination organic substance pyrolytic, wherein this material is mixed with alkaline matter with the ratio of stoichiometry surplus, and pack in the fixed bed reactors of the spherical ceramic formation body that is filled with mechanical movement with the form of suspension.Because the method is at high temperature to decompose, so need energy, have in addition with reaction to generate shortcoming to the disadvantageous accessory substance of environment, also have need special device, device can be because of shortcomings such as pyroreaction are damaged.
In addition, in the fair 6-61373 communique of spy, following method has been proposed, it is the dehalogenation method that has the halogenated hydrocarbon under the situation necleophilic reaction the other side, wherein halogenated hydrocarbon is disperseed with chemical method, under the reaction temperature that is between environment temperature and about 510 ℃, reaction product by making the fine dispersion that obtains like this and nucleophillic attack the other side's chemical reaction and dehalogenation.In the occasion of implementing below 250 ℃, following shortcoming is arranged according to the method: with the necleophilic reaction dehalogenation time, the increase of certain polystream and furans is arranged, or generate the new toxic byproduct that has, also have the inefficient shortcoming of dehalogenation in addition.
As mentioned above, any scheme of prior art all has following problem: or operating difficulties, energy cost is too high, or resolution process needs the time, or when handling with danger, perhaps produce the new toxic byproduct that has and maybe can constitute the accessory substance of global warming reason.
Under these circumstances, wish to finish a kind of like this decomposing process of dioxin consumingly, it should be that special device or high temperature heating etc. are special handles and do not produce under the situation of certain accessory substance that toxic byproduct maybe may cause global warming not needing, can decompose the easy method of handling dioxin, preferably, can also prevent that harmful heavy metal strippings such as cadmium or lead are to outside.
The present invention is exactly in view of such social demand, its problem provides a kind of decomposing process of object being treated (above-mentioned flying dust etc.) of Han dioxin, this method safety and simple and easy, do not needing excessive energy, and do not need special device, and not producing new toxic by-products or environment aspects such as global warming are had makes dioxin decompose under the situation of dysgenic accessory substance, preferably can also prevent the heavy metal stripping that is harmful to, and can effectively utilize the object being treated after the processing.
The 1st, the present invention relates to a kind of decomposing process of dioxin, by making dioxin contained in the object being treated be in Ge Liya reagent state, make decomposition of De dioxin or dechlorination in the object being treated, it is characterized in that this method comprises following operation: the dehydration procedure of removing the moisture content of the object being treated that contains dioxin, in the object being treated that obtains by above-mentioned dehydration procedure, add the mixed processes of mixed magnesium powder, the promotion liquid that the dioxin that is in Ge Liya reagent state in the object being treated that is obtained by above-mentioned mixed processes is played the promotion liquid of reduction reaction with interpolation adds operation.
The 2nd, the present invention relates to the decomposing process of foregoing invention De dioxin, it is characterized in that, before above-mentioned mixed processes, have the heating process of heating object being treated afterwards and with mixed processes at least 1 moment simultaneously.
The 3rd, the present invention relates to the above-mentioned decomposing process of respectively inventing each De dioxin, it is characterized in that, adding the operation while and/or carrying out above-mentioned heating process afterwards with promotion liquid.
The 4th, the present invention relates to the above-mentioned decomposing process of respectively inventing each De dioxin, it is characterized in that, add in any of operation at above-mentioned mixed processes, above-mentioned heating process and above-mentioned promotion liquid, add the heavy metal stripping and prevent agent.
The 5th, the present invention relates to the above-mentioned decomposing process of respectively inventing each De dioxin, it is characterized in that, in above-mentioned dehydration procedure and/or above-mentioned heating process, use the calcium oxide of calcium oxide or coating oil.
The 6th, the present invention relates to the above-mentioned decomposing process of respectively inventing each De dioxin, it is characterized in that, add in the operation at above-mentioned promotion liquid, make water, the alkali metal compound aqueous solution, aquae hydrogenii dioxidi, detergent water, 1 yuan or polyatomic alcohol water solution, the organic sequestering agent aqueous solution at least a kind.
The 7th, the present invention relates to the decomposing process of each De dioxin in above-mentioned the 4th～6 invention, it is characterized in that above-mentioned heavy metal stripping prevents that agent from being at least a kind that selects from the salt of zeolite, phosphorus compound or organic sequestering agent.
The 8th, the present invention relates to the above-mentioned decomposing process of respectively inventing each De dioxin, it is characterized in that above-mentioned object being treated is the flying dust that pollutes from the You dioxin, burn at least a kind that selects the group that ash, mud or greasy filth the like waste and soil constitutes.
The working of an invention mode
Then embodiments of the present invention are described.
About the present invention, the resolution process of said dioxin means the dechlorination that carries out dioxin, becomes avirulent compound, and then in the degree that changes this compound skeleton self, resolves into more low molecular avirulence compound.
About the present invention, said dioxin, be to handle method especially as equalling into No. 105 “ dioxin countermeasure of 11 years laws " the “ dioxin of regulation in the 2nd " (so-called dioxin also has in this specification to be called " narrow sense De bioxin ") and " PCB of coplane " carry out the expression of general name and used.
In above-mentioned narrow sense De dioxin, comprise many chlorodiphenyls and Dui bioxin and polychlorinated dibenzo.
In the above-mentioned narrow sense De dioxin, in many chlorodiphenyls and Dui bioxin, comprise tetrachloro dibenzo Dui bioxin, pentachloro-dibenzo Dui bioxin, chlordene dibenzo Dui bioxin, heptachlor dibenzo Dui bioxin and eight chlorodiphenyls and Dui bioxin.
In addition, in the above-mentioned narrow sense De dioxin, in polychlorinated dibenzo, comprise tetrachloro dibenzofurans, pentachloro-dibenzofurans, chlordene dibenzofurans, heptachlor dibenzofurans and eight chlorodiphenyls and furans.
The PCB of coplane refers to the isomers that the Yu dioxin has same toxicity in the Polychlorinated biphenyls (PCB), be on the ortho position (2,2 ', 6 and 6 ') not with substituent isomers (no ortho position body), having 1 to replace the isomers (an ortho position body) of chlorine and having specific among the isomers (two ortho position bodies) of 2 replacement chlorine, Yu dioxin to have same flat structure on the ortho position on the ortho position.Comprise 3,4 as no ortho position body, 4 ', 5-tetrachloro biphenyls etc. comprise 2,3,3 ', 4,4 '-pentachlorodiphenyl etc. as an ortho position body, comprise 2,2 ', 3,3 ', 4,4 ' as two ortho position bodies, 5-heptachlor biphenyl etc.
In the present invention; the mensuration of bioxin content (concentration), according to " relating to the general discarded object of special management and the calibration method of the benchmark of the discarded object that administers upon an estate especially " and Japanese Industrial Standards' " assay method of the dioxin in the exhaust and the PCB of coplane " in No. the 6th, the Health and human services department bulletin that makes No. 1 (putting down on January 14th, 12) based on Health and human services department (putting down on January 14th, 12).The formulation on September 20th, 11 of JIS K 0311 flat one-tenth) method of record is carried out in.
In above-mentioned JIS regulation, as the index of above-mentioned each toxicity of compound of expression, stipulated with 2,3,7, the toxicity of 8-tetrachloro dibenzo Dui bioxin (TeCDD) is as 2,3,7 of benchmark, 8-TeCDD toxicity coefficient of equivalent (TEF) (with reference to table 2) and 2,3,7,8-TeCDD toxicity equivalent (TEQ) (with reference to table 3) of equal value.In its specification, by the method for its standard as expression toxicity.
Specifically, based on the said determination result,, calculate the toxicity equivalent of dioxin by following formula with reference to the table 1 and the table 2 of corresponding Ge dioxin toxicity coefficient of equivalent (TEF).
Toxicity equivalent (the toxicity summation of contained De dioxin in the object being treated: ng-TEQ/g-dry)=TEF of concentration ng/g-dry * Ge dioxin of Ge dioxin of ∑ ()
When the implication of the term of understanding the Ge Liya reagent state that relates to the present invention's use, refined reagent describes self in the plaid matching, and the dechlorination function of refined reagent describes in the plaid matching.
Ge Liya reagent represents that with general formula R MgX its general title is an alkyl magnesium halide.Ge Liya reagent obtains halogenated alkyl with the magnesium metal reaction in absolute ether, this is by known.Ge Liya reagent and other compound are reactive high, therefore use in various organic synthesis with its ethereal solution former state.
Via Ge Liya reagent, carry out dehalogenation by reduction, be known in halogenated aryl, but only be that compound with the fluorobenzene degree is as object at most.In addition, owing to when water exists, can not make Ge Liya reagent, so this reduction reaction is to carry out under the state of utmost point strict control in ether.And because the reactive height of Ge Liya reagent, so be defined in the situation of refining material (being single material), nothing but under laboratory level, implementing as object by the dehalogenation of this reduction reaction.
In other words; as long as these methods have the material of denier to be present in the medium; will lose function at once; therefore; because in the problem that field of environment protection often runs into is exactly to contain the composition that makes essential catalyst become invalid after the short time in the mixture, so these methods can not actually be used in field of environment protection.
Particularly also do not know dioxin etc. like that highly stable compound this reaction can take place.Therefore and because moisture in the solid, it is difficult generating this Ge Liya reagent, and also nobody expects being used in the chlorine-containing compound dechlorination in making solid.
The inventor is not limited to these opinions always, in dechlorination, the decomposing process of Dui dioxin are researched and developed, be surprisingly found out that the dioxin in the solid also can be via Ge Liya reagent state dechlorination and resolution process effectively, thereby has finished the present invention.
According to above-mentioned, relate to the said Ge Liya reagent of the present invention state, be the form of the Ge Liya reagent that forms by the reaction of the dioxin that contains in the object being treated and magnesium dust.
Ge Liya reagent is unusual unstable compounds as mentioned above, therefore be not easy to confirm its existence in object being treated, but under the situation that adds moisture reaction promotion liquid,, can understand following reaction has taken place by dechlorination having taken place and having judged by the compound that reaction result analyzes.
Now with the mechanism of this reaction, describe with the dehalogenation reaction mechanism contrast of always known halogenated aryl nucleophilic substitution.
It is generally acknowledged that halogenated aryl is to OH
-, OR
-, NH
3And CN
-The reactivity of such nucleophile is very not enough (Morrison's work " organic chemistry (descending) the 6th edition, he translates Chinese and Western, on April 1st, 1998, the Tokyo chemistry is issued with the people "), must high temperature for reacting, the reaction condition of high pressure.
Specifically, the reaction condition of chlorobenzene is that in 6～8%NaOH aqueous solution, 350 ℃, 300 air pressure react be expressed from the next (with reference to Chemical formula 1)
Chemical formula 1
Because when using this necleophilic reaction in the such background, the decomposition of Zai dioxin (or dechlorination reaction), efficient is very low, it is hopeless to curtail expenditure.
On the other hand, when carrying out the dechlorination reaction by the halogenated aryl dechlorination of the present invention, as described below via the reduction reaction of Ge Liya reagent, the example of now enumerating chlorobenzene describes.
Chemical formula 2
Under the situation of absolute ether in case in chlorobenzene, add magnesium, just generate above-mentioned Ge Liya reagent.If then add water, then Ge Liya reagent and water react generation benzene at once, reduction reaction termination (with reference to Chemical formula 2)
Study above-mentioned mechanism at dioxin again.
Under 25 ℃, to the flying dust (of Han dioxin dioxin concentration 7.0ng-TEQ/g-dry, moisture content is below 0.01%) add magnesium dust 2g among the 100g, homogeneous stirs.Add water 60ml then, fully stir.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 5.5ng-TEQ/g-dry in the reactant.
Enumerate 2,3,7 in the bioxin, an example of 8-tetrachloro bioxin describes this mechanism.In addition,, therefore can not detect the Ge Liya reagent of intermediate, but judge, can infer and carry out following reduction reaction (with reference to chemical formula 3 and chemical formula 4) by reaction product because the organic metal body (halogenated aryl magnesium) of intermediate reacts at once with water.In addition, also be to judge by reaction product, can think that skeleton partly also decomposes simultaneously.
Chemical formula 3
Deng
Chemical formula 4
Deng
Evidence as this reaction, by the nucleophilic substitution that can't check replacing body and be heated to 200 ℃ by the OH that generates among the nucleophilic substitution result shown in the following formula (with reference to chemical formula 5) and keeping detecting the also unconverted substantially situation of data among 6 hours the result of nucleophilic substitution product, can judge the halogenated aryl compound that dioxin etc. does not take place.
Can judge according to above-mentioned, in the present invention, by the reduction reaction via Ge Liya reagent state, dioxin has carried out dechlorination and decomposition.
Chemical formula 5
Deng
Through the moisture content in the object being treated of dehydration procedure drying, can obtain according to the method for record in No. the 6th, the above-mentioned Health and human services department bulletin.That is, put down in writing in " adjustment of (2) ウ (ア) test portion " as " subordinate list 1 (No. 1 relation) " in the above-mentioned bulletin, get the about 40g of object being treated, correct weighing (getting the initial stage weight of making object being treated).This object being treated was put in drier cold 30 minutes after 2 hours in drying below 110 ℃ more than 105 ℃, obtained the weight (getting the residual weight of making object being treated) of residuals then.And obtain moisture content in the object being treated with following formula.
Moisture content in the object being treated (%)=[{ (the initial stage weight of object being treated)-(the residual weight of object being treated) } ÷ (the initial stage weight of object being treated)] * 100
Make moisture content in the object being treated of dehydration procedure of the present invention dehydration below 1%, be preferably below 0.1%, special good is below 0.01%, but this is for making dioxin be in the roughly target that Ge Liya reagent state constitutes.
Soil beyond the mud contains the moisture content of 5～80 weight % usually, and mud contains the above moisture content of 80 weight %.On the other hand, the moisture content amount of flying dust and burning ash is roughly below the 10 weight %.
Thereby the present invention was necessary the moisture content containing ratio is dried to below the above-mentioned target before magnesium dust is added, being mixed in the object being treated.
The moisture content of flying dust etc. also has below the 0.1 weight %, and can not carry out dehydration procedure this moment, and order is advanced to mixed processes.
Moisture content in will object being treated goes to the outside by removing in the object being treated fully, so long as dioxin and magnesium dust can form Ge Liya reagent state, stays in the object being treated system also harmless.
As its means, consider to add dehydrating agent or drier, the method that the periphery of You dioxin is removed moisture content substantially.
Dehydration rate is a reference value value, also must guarantee Ge Liya reagent state at last, as making its definite method, take sample by object being treated, hold the wherein containing ratio of contained dioxin, this object being treated is used the dehydration means, use heater means by situation, the mixed magnesium powder adds and handles promoter, analyzes the object being treated that finally obtains, hold the dechlorination of dioxin or the situation of decomposition, again with dehydration conditions, heating condition, the addition of magnesium, handle the adding proportion of promoter and hold data as parameter, the various conditions of experiment decision, more than just constituted suitable method.
Concrete decomposing process just can be further clear and definite by embodiment described later, but the present invention is not limited by it.
As the dehydration means of dehydration procedure, consider to have the method for heating, the method for vacuum attraction, the method for adding dehydrating agent.In heating and vacuum attraction method, must be cautious of doing and make that the De dioxin disperses in the object being treated.
As the dehydrating agent or the drier of dehydration means, but example goes out calcium oxide, magnesia, silica gel, absorbent polymer etc.Also can be with more than one combinations wherein.For example, the soil after will handling as agricultural with soil, civil engineering with soil etc. and the occasion that is used selects these dehydrating agents or drier not to have obstacle.
In above-mentioned dehydrating agent or drier, calcium oxide has heat effect as shown in the formula such and water reaction heating, in utilization more thereafter, except the problem that is alkalescence, can utilize under the situation that does not produce special obstacle, and it is preferred setting out thus.
The calcium oxide that uses in dehydration of the object being treated of water content or drying wishes to add the weight (with the calcium oxide of moisture content amount with the equivalent a great deal of) of 3 times of degree of water content.
The magnesium dust that adds in the mixed processes can use commercially available.Powder size can preferably be used more than 40 orders, more than better 100 orders.In addition, the combined amount of magnesium dust is to form the necessary amount of Ge Liya reagent state between dioxin and magnesium, by sampling, hold the containing ratio that contains the De dioxin in the object being treated, finally set according to the mode more than bioxin becomes equivalent, but for measuring essential a lot of expense and time of dioxin, have any problem, therefore add superfluous greatly magnesium dust usually and measure homogeneous mixing after a little while.
In a word, the concentration of De bioxin in the object being treated is hundreds of ng-TEQ/g-dry (if it is expressed as tens of mg/g-dry with total concentration) to the maximum, and every 1g object being treated is number+ng equivalent quite.If when representing with the magnesium dust of equivalent, quite tens of ng.Make ten times of equivalents even get, also below 1mg.To in the 1g object being treated, homogeneous mixing 1mg be quite difficult (therefore device also must try every possible means), normally add superfluous greatly magnesium dust.That is, add with scope with respect to object being treated 0.01 weight %～10 weight %.Add also passablely more than it, but expense rises, when very few then homogeneous mix difficulty, resolution ratio takes place to be reduced.This is preferably 0.1 weight %～5 weight %.
In addition, mixed method can be used always known various means.Mechanical mixture is arranged, and air-flow mixing etc. wherein as mechanical mixture, can be used spiral agitator, inclined to one side shell mixer (ヘ Application シ エ Le ミ キ サ one), ball mill, swinging mixer etc.As the air-flow mixing method, make heated air (N
2) and the method for the winding-up object being treated that falls together of magnesium dust.Recommendation will heat with hybrid combining to get up to carry out.
After implementing dehydration and heating simultaneously, the method for mixing heats and the method for mixing, the method for enforcement heating before or after mixing, the method that these methods are combined etc. after dehydration is arranged simultaneously, can select according to object being treated is suitable.
Heating condition is not done special restriction, but set out, be preferably below 250 ℃, be more preferred from more than 200 ℃ by the viewpoint of energy consumption.
In addition, in the occasion of carrying out dehydration procedure and heating process with calcium oxide, the processing time was about 3 minutes～30 minutes degree usually in 30 minutes.
In addition, calcium oxide has the function of heating when absorbing water, therefore in above-mentioned dehydration procedure and above-mentioned heating process, preferably uses the calcium oxide of calcium oxide or oil coating.In addition, the magnesium dust of interpolation himself is to the plant effective composition of growing.Therefore mixed proportion is added also harmless by many purposes.
The calcium oxide that oil applies can make it dehydration in dehydration procedure, then do not have exothermic reaction when adding in the object being treated of dewatering state, but then can react and make it heating if add following promotion liquid.
The present invention adds in the operation at the promotion liquid that adds the promotion liquid that the dioxin that is in Ge Liya reagent state is played reduction reaction, the promotion liquid that adds is moisture basically, make between the dioxin (with reference to chemical formula 3) that is in Ge Liya reagent state and the water and play reduction reaction, change into the compound (with reference to chemical formula 4) of various dechlorination states, carry out dechlorination.Can also confirm that ， dioxin basic framework multiring structure self partly is decomposed between this stage of reaction, changes into toxicity more low molecular compound low or that toxicity is extremely low.
Feature of the present invention just is to carry out this reduction reaction.Can carry out this reduction reaction about contained De dioxin in the object being treateds such as soil and not be identified as yet, and the present invention achieves and becomes possibility.The new effect of confirming is, by this reduction reaction, generate in the time of can not generating the nucleophilic substitution of Bi dioxin dechlorination method De dioxin toxicity higher, additional hydroxyl De dioxin etc. (with reference to chemical formula 5).
Add in the operation (so-called reduction reaction promotion operation) at promotion liquid of the present invention, can make the aqueous solution, the organic sequestering agent aqueous solution at least a kind of the aqueous solution, detergent water, 1 yuan of water, alkali metal compound or polyalcohol promote liquid as reduction reaction.
This reduction reaction promotes the amount of liquid, dioxin with respect to Ge Liya reagent state contained in the object being treated, be 2 times more than the equivalent, but be that viewpoint very trace and that added superfluous greatly magnesium dust etc. is set out, add superfluous greatly amount of moisture usually by dioxin.Promptly same with magnesium dust, be the scope of 1 weight %～10 weight % with respect to object being treated.
In the present invention, the calcium oxide that uses calcium oxide and oil to apply is implemented the occasion of heating process, reacts for making they and water, is necessary to add the moisture content amount of the 1 times of equivalent～20 times equivalent (if being expressed as 0.3 times～6 times weight with weight) that is equivalent to its addition again.Be more preferred from 2 times of equivalent～10 times equivalents.
The present invention also has such feature: unnecessary special heater and pressue device, react under normal temperature, normal pressure or approaching with it condition.The result is, according to the present invention, do not want excessive energy with regard to the dechlorination of Shi dioxin be decomposed into possibility.
Above-mentioned promotion liquid is the occasion of the alkali metal compound aqueous solution, is improving operating aspect, can play the effect of removing the oil that applies on the calcium oxide.Washing agent, other promoter also have same effect.
And, to as being used for the oil that oil applies, be not particularly limited, if use vegetable oil, then after processing, be used for the processing of soil, after processing,, can effectively utilize directly as agro-farming usefulness.But preferred vegetable oil example goes out corn oil, rapeseed oil, coconut oil, palm oil, soybean oil, castor oil etc.
As alkali metal compound, but preferred exemplary goes out the alkali metal compound of the alkali metal salt of inorganic acids such as carbonic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, silicic acid, alkali-metal hydroxide and organic sequestering agent etc.As these alkali metal, but consider that by price example goes out sodium, potassium.Particularly with the occasion of soil as object, wish sylvite with plant three nutrients, contain occasion more than the heavy metal at flying dust etc., more wish to use to combine phosphoric acid, phosphorous acid, the alkali metal salt of hypophosphorous acid and the alkali metal compound of organic sequestering agent that generates insoluble substance with heavy metal.That is, can preferred exemplary go out potash, sodium carbonate, sodium metasilicate, sodium chloride, sodium nitrate, potassium phosphate, sodium phosphate, potassium phosphite, sodium phosphite, potassium hypophosphite, sodium nitrate etc.
As washing agent, use any all can, but example goes out neutral detergent, acid detergent, alkaline detergent etc.
Can use various alcohol as alcohol, but 1 yuan of alcohol example goes out isopropyl alcohol, but and the polyalcohol example goes out ethylene glycol.At least a interpolation of its aqueous solution is mixed in the above-mentioned object being treated to good.
Mix by this interpolation, following effect is arranged, the resolution ratio of Shi dioxin improves, and the above-mentioned object being treated after the resolution process can also be done utilizations again such as landfill simultaneously.
Processing object handling with method of the present invention for example in the flying dust, contains harmful heavy metals such as cadmium, lead sometimes, and such flying dust is discarded when outdoor, can cause new pollution problem.
In the present invention, for sorption, catch these poisonous metals and make it not stripping, preferably use the heavy metal stripping to prevent agent to outside.Prevent agent as this heavy metal species stripping, can use the alkali metal salt (salt of phosphorus compound) of zeolite or organic sequestering agent and phosphoric acid, phosphorous acid, hypophosphorous acid.
Prevent the zeolite that agent is used as this heavy metal species stripping, be generally hydrosilicate, but in the present invention, be not with natural zeolite or synthetic zeolite, and suitable use artificial zeolite.This artificial zeolite be with coal ash etc. as the synthetic zeolite of raw material, it be different from must pure to a certain degree raw material (silicic acid, aluminium hydroxide etc.) synthetic zeolite.And in this artificial zeolite, containing the intermediate product and the unburned carbon composition that are not to constitute fully zeolite, the purity of zeolite is in synthetic zeolite and natural zeolite position intermediate.Thereby the impurity (intermediate product, unburned carbon composition) of this artificial zeolite because of being contained has useful characteristics such as sorption property and ion-exchange performance.In addition, cation exchange capacity and natural zeolite are equal and even 3 times degree.Have, its manufacture method of this artificial zeolite has sodium type, swage, calcium type, plumbous type, silver-colored type, magnesium type etc., and all is fit to again, but from secure context and consideration in price, the artificial zeolite is the most suitable with the calcium type.
In above-mentioned zeolite, the swage zeolite can not only prevent the stripping of heavy metal, and can promote the capacity of decomposition of dioxin, and is therefore special good.
Prevent the organic sequestering agent that agent is used as this heavy metal species stripping, ethylenediamine tetra-acetic acid or aminodithioformic acid etc. are arranged, form chelate compound, prevented the stripping of heavy metal with heavy metals such as cadmium, lead.
Object being treated of the present invention can be flying dust, burning ash, mud or greasy filth the like waste and the soil that independent separately You dioxin pollutes, but also can be with the multiple combination of suitable object being treated as handling object.For example because burn grey alkali metal containing composition, so if with the combination of object being treated such as mud, then can omit or reduce the interpolation that promotes liquid.
Flying dusts after obtaining the De dioxin like this and decomposing etc. are not suitable for being directly used in landfill during for alkalescence sometimes, neutralize in the middle of therefore preferably acid being added to flying dust etc.As the acid of neutralization usefulness, can enumerate organic acids such as inorganic acid such as carbonated water, sulfuric acid water or citric acid.
Moreover, in order to breed plant, must prevent the harm that calcium too much causes in the middle of the agro-farming soil etc., promptly prevent magnesium deficiency, to this, wish to contain magnesia or peromag.In addition, for preventing magnesium deficiency, the magnesian mixture that calcium oxide that preferred oil applies and oil apply, the relative calcium oxide of magnesian amount this moment are 5～50% for good.
The form of decomposing process of the present invention then, is described by embodiment.
[embodiment]
The present invention is described by the following examples, but these are examples, scope of the present invention are not done any qualification.
[embodiment 1]
Be the flying dust (dioxin concentration of 2.3% Han dioxin with moisture content: 7ng-TEQ/g-dry) 100g adds beaker, puts it in the large-scale drier that fills drier (silica gel), preserves about 2 weeks.Moisture content in the dried flying dust is 0.15%.At room temperature add magnesium dust 2g, homogeneous stirs.Add water 60ml and fully stirring then.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 5.8ng-TEQ/g-dry in the reactant.Survival rate is 80% (survival rate (%)=(every dry weight De dioxin toxicity equivalent in the reactant)/(every dry weight De dioxin toxicity equivalent in the initial stage flying dust) * 100).
[embodiment 2]
With moisture content the flying dust (dioxin concentration of 2.3% Han dioxin: after 7ng-TEQ/g-dry) 100g adds the flat container of SUS system, the SUS container made is put into the airtight container of 2 relative apertures.By logical about 1 week of dry air of closed container one side's hole, make the flying dust drying.Moisture content in the flying dust of dry back is below 0.01%.At room temperature add magnesium dust 2g, homogeneous stirs.Adding water 60ml then fully stirs.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 5.5ng-TEQ/g-dry in the reactant.Survival rate is 79%.
[embodiment 3]
Be the flying dust (dioxin concentration of 2.3% Han dioxin with moisture content: 7ng-TEQ/g-dry) 100g adds after the flat container of SUS system, place airtight container to be set on 90 ℃ the electric hot plate SUS container made that adds flying dust, put it in the relative closed container in two holes, hole by airtight container one side feeds N2 gas, the SUS container made of flying dust of will packing into simultaneously keeps down about 1 round the clock in 90 ℃, carries out drying.Moisture content in the dried flying dust is below 0.01%.Keep placing the state on the electric hot plate and adding magnesium dust 2g, homogeneous stirs.Then, be heated to 90 ℃ water, fully stir.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 2.5ng-TEQ/g-dry in the reactant.Survival rate is 36%.
[embodiment 4]
Similarly to Example 1, will carry out the flying dust (dioxin concentration of the dry Han dioxin of moisture content 0.01% below: 7ng-TEQ/g-dry) 100g be set at keep about 1 hour on 90 ℃ the electric hot plate after, add magnesium dust 2g, the homogeneous stirring.Adding water 60ml then fully stirs.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 3.1ng-TEQ/g-dry in the reactant.Survival rate is 44%.
[embodiment 5]
Similarly to Example 2,90 ℃ the flying dust of in closed container drying being crossed adds in the ball mill container that is warmed to 150 ℃ in advance, adds magnesium dust 2g, and homogeneous stirs.Adding water 60ml then fully stirs.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 2.2ng-TEQ/g-dry in the reactant.Survival rate is 31%.
[embodiment 6]
In embodiment 2, when adding magnesium dust 2g, add the calcium type artificial zeolite that the heavy metal stripping prevents agent again.Other is identical.Implement the dissolution test of heavy metal then.It the results are shown in table 1.
[embodiment 7]
In embodiment 2, will promote that liquid changes to 2% aqueous solution that the heavy metal stripping prevents the sodium phosphite of agent.Other is identical.Implement the dissolution test of heavy metal then.It the results are shown in table 1.
[embodiment 8]
In embodiment 2, will promote that liquid changes to 2% aqueous solution that the heavy metal stripping prevents the thiocarbamic acid sodium of agent.Other is identical.Implement the dissolution test of heavy metal then.It the results are shown in table 1.
Table 1 heavy metal dissolution test result is (except that content, mg/l)
| A reference value mg/l | Initial stage content ppm in the object being treated | Embodiment 3 mg/l | Embodiment 6 mg/l | Embodiment 7 mg/l | Embodiment 8 mg/l | |
| Cadmium or its compound | ＜0.3 | 61 | ＜0.001 | ＜0.001 | ＜0.001 | ＜0.001 |
| Lead or its compound | ＜0.3 | 1180 | 0.85 | 0.15 | 0.10 | ＜0.05 |
| 6 valency chromium compounds | ＜1.5 | 120 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 |
| Arsenic or its compound | ＜0.3 | 7.9 | ＜0.03 | ＜0.03 | ＜0.03 | ＜0.03 |
| Mercury or its compound | ＜0.005 | 4.3 | ＜0.0005 | ＜0.0005 | ＜0.0005 | ＜0.0005 |
| Selenium or its compound | ＜0.3 | ＜0.03 | ＜0.03 | ＜0.03 | ＜0.03 | |
| The heavy metal stripping prevents agent | Zeolite | Phosphite | Organic sequestering agent |
[embodiment 9]
With moisture content is 2.3%, the flying dust (dioxin concentration of Han dioxin: 7ng-TEQ/g-dry) 100g adds in the beaker of the adiabatic material of outside use, adds calcium oxide 8g as drier, fully stirs.The temperature of flying dust rises to 50 ℃.Moisture content in the dried flying dust is below 0.01%.Add magnesium dust 2g at once, homogeneous stirs.Add water 60ml then, fully stir.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 2.8ng-TEQ/g-dry in the reactant.Survival rate is 40%.
[embodiment 10]
With moisture content is 2.3%, the flying dust (dioxin concentration of Han dioxin: 7ng-TEQ/g-dry) 100g adds in the beaker of the adiabatic material of outside use, adds calcium oxide 8g as drier, fully stirs.The temperature of flying dust rises to 50 ℃.Moisture content in the dried flying dust is below 0.01%.Add magnesium dust 2g and the conduct heating calcium oxide 25g with exothermic mixture at once, homogeneous stirs.Add water 60ml then, fully stir.The temperature of mixture rises to 100 ℃.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 1.8ng-TEQ/g-dry in the reactant.Survival rate is 26%.
[embodiment 11]
With moisture content is 2.3%, the flying dust (dioxin concentration of Han dioxin: 7ng-TEQ/g-dry) 100g adds in the beaker of the adiabatic material of outside use, adds calcium oxide 8g as drier, fully stirs.The temperature of flying dust rises to 50 ℃.Moisture content in the dried flying dust is below 0.01%.Add magnesium dust 2g and the conduct heating calcium oxide 25g with the vegetable oil coating surface with exothermic mixture at once, homogeneous stirs.Add 2% alkali wash water 60ml then, fully stir.The temperature of mixture rises to 100 ℃.Assaying reaction thing De dioxin concentration then.De dioxin concentration is 1.6ng-TEQ/g-dry in the reactant.Survival rate is 23%.
As mentioned above, the present invention can provide a kind of Han dioxin flying dust, burn the decomposing process of De dioxin in ash, mud or greasy filth the like waste and the soil solid such as (object being treateds).According to decomposing process of the present invention, safe and simple and easy, do not need excessive energy, do not need special device in addition, and new toxic by-products does not take place, perhaps make greenhouse effects of the earth etc. that environment is had dysgenic some accessory substance, and can decompose by the Shi dioxin, preferably can also prevent the stripping of the heavy metal that is harmful to, and can effectively utilize the object being treated after the processing.
The toxicity coefficient of equivalent of table 2 dioxin
| Isomers | TEF(1988) *1 | TEF(1997) *2 | |
| PCDDs | 2，3，7，8-TeCDD | 1 | 1 |
| 1，2，3，7，8-PeCDD | 0.5 | 1 | |
| 1，2，3，4，7，8-HxCDD 1，2，3，6，7，8-HxCDD 1，2，3，7，8，9-HxCDD | 0.1 0.1 0.1 | 0.1 0.1 0.1 | |
| 1，2，3，4，6，7，8-HpCDD | 0.01 | 0.01 | |
| 1，2，3，4，6，7，8，9-OCDD | 0.001 | 0.0001 | |
| Other | 0 | 0 | |
| PCDFs | 2，3，7，8-TeCDF | 0.1 | 0.1 |
| 1，2，3，7，8-PeCDF 2，3，4，7，8-PeCDF | 0.05 0.5 | 0.05 0.5 | |
| 1，2，3，4，7，8-HxCDF 1，2，3，6，7，8-HxCDF 1，2，3，7，8，9-HxCDF 2，3，4，6，7，8-HxCDF | 0.1 0.1 0.1 0.1 | 0.1 0.1 0.1 0.1 | |
| 1，2，3，4，6，7，8-HpCDF 1，2，3，4，7，8，9-HpCDF | 0.01 0.01 | 0.01 0.01 | |
| 1，2，3，4，6，7，8，9-OCDF | 0.001 | 0.0001 | |
| Other | 0 | 0 | |
*1 " TEF (1988) " are represented to be proposed by WHO/IPCS in 1988.
*2 " TEF (1997) " are represented to be proposed by WHO/IPCS in 1997.
The toxicity coefficient of equivalent of the PCB of table 3 coplane
| Isomers | TEF(1993) *3 | TEF(1997) *4 | |
| No ortho position body | 3，4，4′，5-TeCB(#81) 3，3′，4，4′-TeCB(#77) 3，3′，4，4′，5-PeCB(#126) 3，3′，4，4′，5，5′-HxCB(#169) | - 0.0005 0.1 0.01 | 0.0001 0.0001 0.1 0.01 |
| One ortho position body | 2′，3，4，4′，5-PeCB(#123) 2，3′，4，4′，5-PeCB(#118) 2，3，3′，4，4′-PeCB(#105) 2，3，4，4′，5-PeCB(#114) 2，3′，4，4′，5，5′-HxCB(#167) 2，3，3′，4，4′，5-HxCB(#156) 2，3，3′，4，4′，5′-HxCB(#157) 2，3，3′，4，4′，5，5′-HpCB(#189) | 0.0001 0.0001 0.0001 0.0005 0.00001 0.0005 0.0005 0.0001 | 0.0001 0.0001 0.0001 0.0005 0.00001 0.0005 0.0005 0.0001 |
| Two ortho position bodies | 2，2′，3，4，4′，5，5′-HpCB(#180) 2，2′，3，3′，4，4′，5-HpCB(#170) | 0.00001 0.0001 | - - |
*3 " TEF (1993) " are represented to be proposed by WHO/IPCS in 1993.
*4 " TEF (1997) " are represented to be proposed by WHO/IPCS in 1997.
Claims (9)
1,, the decomposing process of dioxin, by making dioxin contained in the object being treated be in Ge Liya reagent state, make decomposition of De dioxin or dechlorination in the object being treated, it is characterized in that this method comprises following operation: remove the dehydration procedure of the moisture content of the object being treated that contains dioxin, in the object being treated that obtains by above-mentioned dehydration procedure the mixed magnesium powder mixed processes and add the promotion liquid that the dioxin that is in Ge Liya reagent state in the object being treated that is obtained by above-mentioned mixed processes is played the promotion liquid of reduction reaction and add operation.
2, the decomposing process of the described dioxin of claim 1 is characterized in that, before above-mentioned mixed processes, have the heating process of heating object being treated afterwards and with mixed processes at least 1 moment simultaneously.
3, the decomposing process of claim 1 or 2 described dioxins is characterized in that, is adding the operation while and/or is carrying out above-mentioned heating process afterwards with promotion liquid.
4, the decomposing process of claim 1 or 2 described dioxins is characterized in that, adds in any of operation at above-mentioned mixed processes, above-mentioned heating process and above-mentioned promotion liquid, adds the heavy metal stripping and prevents agent.
5, the decomposing process of claim 1 or 2 described dioxins is characterized in that, in above-mentioned dehydration procedure and/or above-mentioned heating process, uses the calcium oxide of calcium oxide or coating oil.
6, the decomposing process of claim 1 or 2 described dioxins is characterized in that, adds in the operation at above-mentioned promotion liquid, makes the aqueous solution, detergent water, the organic sequestering agent aqueous solution at least a kind of water, alkali metal compound.
7, the decomposing process of the described dioxin of claim 4 is characterized in that, above-mentioned heavy metal stripping prevents that agent from being at least a kind that selects from the salt of zeolite, phosphorus compound or organic sequestering agent.
8, the decomposing process of claim 1 or 2 described dioxins is characterized in that, above-mentioned object being treated is at least a kind that selects the group that constitutes of the discarded object that pollutes from the You dioxin or soil.
9, the decomposing process of the described dioxin of claim 8 is characterized in that, above-mentioned discarded object is flying dust, burning ash, mud or greasy filth.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000166525 | 2000-05-31 | ||
| JP166525/00 | 2000-05-31 | ||
| JP166525/2000 | 2000-05-31 | ||
| JP2000177545A JP2002052373A (en) | 2000-05-31 | 2000-06-13 | Method for decomposition of dioxins |
| JP177545/2000 | 2000-06-13 | ||
| JP177545/00 | 2000-06-13 |
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| CN1330969A CN1330969A (en) | 2002-01-16 |
| CN1238074C true CN1238074C (en) | 2006-01-25 |
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| JP (1) | JP2002052373A (en) |
| KR (1) | KR20010109480A (en) |
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| JP4901268B2 (en) * | 2006-03-31 | 2012-03-21 | 中国電力株式会社 | Method for suppressing elution of harmful trace elements and elution inhibitor for coal addition used therefor |
| CN102266712A (en) * | 2010-03-01 | 2011-12-07 | 中国科学院生态环境研究中心 | Method for inhibiting generation of dioxins |
| JP2012030198A (en) * | 2010-08-03 | 2012-02-16 | Omega:Kk | Reattachment prevention mechanism to soil, such as heavy metal |
| CN105290077A (en) * | 2014-06-16 | 2016-02-03 | 北京精诚博桑科技有限公司 | Method for coprocessing fly ash and landfill leachate |
| CN108101336B (en) * | 2016-11-25 | 2020-09-11 | 中国石油化工股份有限公司 | Drying treatment process for residual activated sludge |
| CN106824983A (en) * | 2017-01-10 | 2017-06-13 | 北京科技大学 | A kind of detoxification of incineration of refuse flyash Zhong bioxin and heavy metal |
| CN113633921B (en) * | 2021-09-08 | 2022-09-27 | 宜辰荣(浙江宁波)环境工程技术有限公司 | Fly ash dechlorination method |
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| KR20010109480A (en) | 2001-12-10 |
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