CN1565676A - Deacidizing and aggradating method on metal surface - Google Patents

Abstract

A method for reducing deposition of the reducible compound in form of itself or component part of the mixture or solution by means of reductive metal is disclosed. Therein, the reducible compound is continuous reduced and immobilized on the continuous machine in situ restored clean surface of fine dispersed reduced metal. The method is useful for chemical reduction of the inorganic compounds or organic compounds, in particular for the detoxification and immobilization field of the toxic materials.

Description

Reduce deposition method on the metal surface

The detailed description of invention

The present invention relates to a kind of usefully in and organic compound inorganic with chemical mode reduction, mainly is useful method in the detoxifcation of toxic material and immobilization field.The reduction decomposition of the poisonous structure by organic compound and the reduction immobilization by poisonous inorganic matter have reduced the potential danger of described toxic compounds significantly.Distinct example is that halogenated organic passes through the detoxifcation that reductive dehalogenation forms corresponding harmless hydrocarbon, with generate corresponding harmless aliphatic derivatives by carcinogenic poly-ring aromatic compounds through hydrogenation, the example of wherein said halogenated organic comprises Polychlorinated biphenyls (PCB) and Duo chlorodiphenyl Bing dioxine or dibenzofuran (Er Evil compounds).Another example is the immobilization that method of reducing produces water-fast heavy metal of passing through of water-soluble heavy metal compound.

Reduction is a kind of very basic chemical reaction, and has obtained detailed description in inorganic chemistry and organic chemistry textbook.Also have a lot of documents mainly about PCB and analog metal (particularly alkali metal) reductive dehalogenation.

Sometimes metal is used separately, but in most cases metal is used with the hydrogen source material is collaborative.According to Australian PL 6474 and PL 9085, with halogenated organic with the mechanochemistry mode by with metal separately or in the presence of the hydrogen source material, grind and destroy.United States Patent (USP) 4 639 309 has provided the example that the sodium of fusion form (promptly being higher than under 100 ℃ the temperature) and potassium use with the sand as the auxiliary agent of the alkali halide of removing formation from the alkali metal surface by friction.This method is similar to the ancient Sa PCB in old-fashioned end dehalogenation method.This method is used the sodium of fusion, but is not added sand etc. under about 300 ℃ temperature in mineral oil.Because all taken place to generate the cracked completely of carbide even carbon in all these methods, the result can not separate the hydrocarbon of correspondence.

Additive method has used reducing metal with dissimilar hydrogen source materials, for example United States Patent (USP) 4 853 040,4 950 833,4 973 783,4 950 833, EP 0099951,0 225 849, DE 34 10 239,199 03 986, CH 668 709, Canadian patent application 20 26 506.These dehalogenation methods all have some important disadvantages.If alkali metal or alkaline-earth metal are used in liquid system, for prevent metal with the competitive reaction of the hydrogen source material more active than halogen compounds in consumed uselessly, the hydrogen source material must be low acid.Thus, simple, cheap alcohol (for example methyl alcohol) can not be used as the hydrogen source material.But low acid hydrogen source material (for example polyethers and Armeen or secondary amine) is very expensive, and causes entire method to become uneconomical.In addition, effective especially and particularly preferred therefrom primary amine can cause the generation of identical with the former halogenated compound at least aminoderivative of toxicity as the hydrogen source material.DE 199 03 986 has described a kind of preferred method, and wherein amine is used as electronics and shifts accelerator and only use with cheap hydrogen source material to be lower than stoichiometric catalytic amount, has suppressed the generation of poisonous aminoderivative thus.Zui You result uses the tertiary amine that can not generate poisonous derivative certainly to obtain in this regard.

The reduction of poly-ring aromatic compounds (for example carcinogenic benzo [a] pyrene) can be carried out on record Birch reaction or its modification, promptly in liquid ammonia under the temperature between-33 ℃ to-50 ℃ or be said to be form what is called " solvated electron " amine in the presence of carry out.These methods may be useful in laboratory scale application, but are infeasible for extensive realization, then are infeasible fully in garbage disposal.

According to the present invention, overcome and be used for reducing the above-mentioned shortcoming of method of prior art of organic compound (particularly halogenated organic and poly-ring aromatic compounds).Can be used to reduce inorganic compound according to reduce deposition method of the present invention, be used for realizing respectively removing and immobilization.

Have been found that in the initial action step according to the present invention, before real reduction reaction takes place, reducing metal at first with the optionally complexing of reducible organic compound.

For example, be suspended in the fragment of the sodium in the hydrocarbon solvent and the excessive propyl alcohol immediate response of adding, form the hydrogen of stoichiometric amount, be accompanied by the generation of this process, temperature sharply raises.If only add the reducible organic compound (for example trichloro-benzenes (TCB)) of trace this moment, the generation of hydrogen stops immediately, and the same dramatic temperature rising that still can be observed shows have the exothermic chemical process to take place.There is not appreciable product (for example sodium chloride) to produce.This is a very astonishing phenomenon, because it is on record that sodium and alcohol react very intensely, can not estimate fully only to contain in the solution of TCB of a small amount of low reaction activity containing a large amount of excessive active alcohol of height, sodium can be optionally and the latter reaction, thereby stop any other chemical reaction.In other words, be a side with reducing metal and H-O key, in the disadvantageous competitive reaction with reducing metal and Cl-C key position the opposing party, can not haggle over inactive competitor in advance and can win victory.

In fact, the sodium that is placed in the hydrocarbon solution with micro-TCB and a large amount of excessive alcohol is optionally collected reducible organic compound TCB by TCB at the lip-deep reduce deposition of sodium.This has formed one deck molecular layer, and this molecular layer has stoped the generation of the more substantial unreacted sodium that still is present in below the inhibition molecular layer and the further reaction of the excessive alcohol that equally still exists fully.

First product of the inhibition that produced of aroma system of Fa Xianing and intermetallic interaction looks it is a kind of CT-complex compound thus.Wherein an electronics from metal is transferred on first antibonding orbital of aromatic, but is not to the Cl-C key and form the ion free radical or even as the sodium chloride of visible product.Surprisingly, the inhibition film can not be simply removed by stirring (for example on magnetic stirrer or even add some steel balls).

In view of the above, because the above-mentioned reduce deposition that takes place by the generation complex compound has caused the generation of inhibition molecular layer, thereby suppressed the further reaction of sodium, the concentration of TCB only is reduced to corresponding to the degree of reduce deposition in the lip-deep TCB part of available sodium in the above-mentioned solution.For with whole described TCB and existing sodium complete reaction, according to the present invention, the surface of sodium must be by mechanically being restored continuously in position, thereby realize the reduce deposition that carries out continuously and cause collection fully by the whole TCB that form complex compound.

Similarly interact and also can take place with any other reducible organic compound the time, wherein " reducible " refers to when complex compound generates preferentially and optionally wins electronics and transfer to the ability of low-yield track from reducing metal.This compounds is unsaturated aliphatic or alicyclic compound, aromatic (particularly poly-ring aromatic compounds), halide, aldehydes or ketones and nitro compound.

Can also know clearly that from this phenomenon electronics must be set up from transfer to the metal of the current potential with corrigendum on the metal with more negative standard electrode potential and the same mechanism that causes producing the inhibition covered effect in electronegative metals.This mechanism on record really for example promptly known from electro-plating method, but also never is used for according to the present invention in the immobilization of the heavy metal of contaminated materials.Two kinds of methods (being the formation of reducible organic complex compound and the electro-deposition of reducible inorganic compound) can be summarized by inorganic or organic reducible compound " reduce deposition " this saying on the metal surface.

Find according to these, can easily summarize the immobilization basic principle of reductive dehalogenation and the heavy metal (being the copper of form for example) of TCB of the present invention by way of example with mantoquita as pollutant.

In liquid system, collect and reduce as reducible organic TCB by the method that forms complex compound on the metal surface of recovering method that carry out, that produce benzene with chemical mode at the mechanical type continuous in-situ, can realize with the stirring system of any generation high shear force, and the preferred high-speed dispersion equipment of this system for example is equipped with the IKA Ultra-Turrax T25 of S 25 N-18G dispersal devices.Use this equipment, Duo 10% sodium by in 10 minutes, adding, even under the minimum mixing velocity of 11000rpm/min, also can be less than 10 minutes with the interior TCB that collects fully in the liquid solution than stoichiometric amount.

Sodium and potassium are ductile, and can be at room temperature between the rotor of dispersing apparatus and stator part assemble, hindered freely the passing through of particle of fine dispersion thus.In this case, the major part of jitter time need be used for the coarse granule of sodium that when beginning existed and is dispersed to and can be easily passes through between the rotor of S 25N-18G dispersal device and stator.But, in Retsch planetary type ball-milling S1,, at room temperature only needed about 3 minutes can collect whole PCB by grinding the sodium of (for example grinding with for example grinding aid of 0.5% octadecylamine) fine dispersion preparation, on powdery aluminium, magnesium or calcium, iron (the preferably iron powder that makes by carbonyl iron), active carbon, graphite, unreducible plastic powders or bead analogs such as (for example polyethylene, polypropylene) with 2: 1 ratio.If after the above-mentioned time, stop dispersal device, can produce spontaneous being separated, the sample of the limpid and colourless liquid phase of taking out with syringe does not contain the TCB that gas phase chromatogram (GC) can detected amount.

The mixture through grinding of reducing metal and above-mentioned powder carrier component is spontaneously inflammable, and necessary handled is preferably handled in nitrogen.In order to obtain better handling properties, can the mixture that contain highly active reducing metal be coated.This can be by grinding with temporary transient deactivation organic material (for example solid paraffin) or described solid paraffin being realized in spraying (under nitrogen) on the described mixture.

The use of the combination of the granulated metal (for example iron and aluminium) that highly active metal (for example lithium, sodium and potassium) and reactivity are lower is significant, can be used for adsorbing and total metal surface that after this electronics shifts because do like this to have strengthened, thereby help on bigger metal surface reducing immobilization quickly by complexing.

Though graphite exhibit metallic, active carbon are mainly as adsorbent, its effect is to help absorptive collection TCB, to form complex compound fast on the surface of the sodium of sneaking into.

In order to further specify example, through reduce immobilized reducing metal and reducible organic compound TCB complex compound and can be subsequently with the hydrogen source material in position or through by decant, centrifugal or filter in the step of separating of the after separating that carries out and react, thereby generate corresponding hydrocarbon.For example, in order to reclaim mineral oil that PCB pollutes so that reuse, the sodium that uses the Ultra-Turrax dispersing apparatus will be in the stoichiometric amount on the aluminium is dispersed in a few minutes in this liquid.Behind the closing device, solid separates automatically, and clean oil phase can be by decant or centrifugal the recovery.Solid after the separation can be in the reactor that is separating with the hydrogen source material reaction back discarded.

The most cheap but also be that the most active hydrogen source material is a water.Owing to still may have highly active sodium, generally can use the mixture (for example water and methyl alcohol) of the alcohol of lower water of reactivity and cheapness.

If add carbon source material (for example formaldehyde, acetone or carbon dioxide), corresponding alcohol and carboxylic acid will be generated respectively.Certainly, in this case, in complex compound formation step, do not add excessive lithium, sodium or potassium.

If halogenated organic compounds (for example Er Evil compounds) is present in solid mixture or the solid solution as pollutant, can use a kind of abundant mixing apparatus to generate clean metal surface in position continuously, and the shearing force of this equipment is enough high, not only can guarantee the formation of the clean metal surface of recovering continuously, and can guarantee to the effective Mechanical Crushing of coarse component with make contacting fast of described clean metal surface Yu Er Evil compounds (for example being mixed in De Er Evil compounds in vitreous flying dust of incinerator).

The mixing apparatus that meets these requirements be have a very big shearing force smash mill, horizontal or vertical ball mill (for example tower mill of Erich MaxxMill and Kubota), vibrations ball mill, cutting type grinding mill (cutting mill), impact mill or extruder or kneader to pieces.

When (particularly De Er Evil compounds in the flying dust) such as reducible organic matters in collecting solid, the step of decision speed is directly corresponding to the migration velocity of described compound.Er Evil compounds mainly is incorporated into vitreous solid flying dust particle, can easily not be that the complex compound forming process is resultant.For can near in conjunction with after De Er Evil compounds, thereby must be with the fully broken Er Evil compounds that discharges of coarse granule.

It is much longer that the needed time ratio of this process forms the needed time of complex compound.Therefore, definitely be reactive and uneconomic for example, because the hydrogen source material has consumed sodium greatly utterly uselessly according in the presence of the hydrogen source material, flying dust being ground as described in the document of some prior art with sodium.From basic principle of the present invention, very clear, all add more substantial sodium according to passing through of doing of the document of some prior art increases the reason that the effort of dehalogenation speed all failed and is, sodium is hidden in the nature of glass flying dust particle directly contact hydrogen source material and reaction with it before the De Er Evil compounds having an opportunity to attack.Importantly, in the case, the hydrogen source material can not be water or alcohol at all, only produces hydrogen gas because these compounds incite somebody to action the sodium of the amount that consume any existence immediately and fully.

According to basic principle of the present invention, flying dust is only ground (promptly not adding any hydrogen source material) with sodium, and the time long enough that grinds, so that thick flying dust particle discharges the De Er Evil compounds that seals fully, thereby use it for complexing.Although the speed that complex compound generates depends on the collision frequency between free Er Evil compounds and free metal surface certainly, is that coarse granule is pulverized the needed time fully to what have the greatest impact needed total time.This numeral depends on the efficient of milling apparatus fully, and for Retsch mill or tower mill, and this digital scope is for for example from 60 minutes to 90 minutes.Can strengthen coarse grained fragmentation by adding grinding aid, in the case, grinding aid must be not as the compound that can not be used as the hydrogen source material.Preferred grinding aid is a long-chain amine, octadecylamine for example, it is shaped as sphere, amino group by around the hydrocarbon chain protection.

To be present in De Er Evil compounds in the solid matrix in order moving, can to add a small amount of atent solvent, this solvent is strengthened the release of Er Evil compounds by extraction.But being added in the mill of liquid flux may cause caking.Therefore, the most handy solid solvent (for example form be powder or ball, for example polyethylene, polyacrylic inert plastic etc.) replace liquid flux.The chemical affinity of described organic polymer Dui Er Evil compounds is than inoganic solids height.

In solid, generally can not separate reducing metal and reducible organic complex compound.In view of the above, must in the mixture of the grinding that contains described complex compound, carry out with the end reaction (generating corresponding hydrocarbon and hydrocarbon derivative respectively) of hydrogen or carbon source material.Carry out in the same equipment that this reaction can ground in treatment step subsequently, also can in the mixing apparatus of another series connection, carry out (preferably).

The mixing apparatus of an independent series connection has in the advantage that allows greater flexibility aspect the processing thermal control.When the complex compound that will form during with the hydrogen source substance reaction that is made of for example water and methanol mixture, must dissipate a large amount of reaction heat in the presence of excessive sodium at short notice.This can more easily use the mixing apparatus of the independent series connection of film reactor effect to handle, thereby realizes effective and the heat dissipation of control fully.Thus can be to carrying out more time-consuming solvolysis subsequently in the independent equipment of a large amount of treated solid that in less relatively initial mixing apparatus (for example tower mill), produces in appropriate design, wherein, as an extra advantage, can be in the scope that residual reagent and product can not be volatilized with temperature maintenance.

If handle the thick especially material that contains reducible compound according to the present invention, before itself and reducing metal are transported to follow-up essence mixing or milling apparatus together, at first in pregrounding equipment, this contaminated materials are carried out preliminary treatment and may have advantage.Handle in this way and can obtain much smaller granularity more economically.Also can significantly improve the efficient of this treatment step by adding grinding aid or organic solvent or its mixture.

The present invention also relates to the electronation of inorganic compound, preferably with the electronation of heavy metal as pollutant.Heavy metal can not resemble organic compound that works and detoxify by degrading, and but, their danger can be reduced to minimum by the immobilization and the chemical fixationization of remarkable its bioavilability of reduction.Although heavy metallic salt is water-soluble, its electronation form (being metal element) is insoluble.Fortunately, all toxic heavy metals all have the reduction potential than alkali metal and alkaline-earth metal and aluminium and iron corrigendum.In view of the above, the heavy metal of ionic species (for example Cd, Pb, Cu and Hg) will be by described reducing metal electronation, thereby produces insoluble heavy metal.The method that is adopted is identical with the description of the reaction of described reducing metal and reducible organic compound.First step is that electronics is transferred to heavy metal compound by reducing metal.Thus, as the product of initial action, generated the heavy metal of one deck chemical deposition on the reducing metal surface, this layer stoped the further reaction on reducing metal surface.In view of the above, only can just can use up the Restore All ability of reducing metal by the former bit recovery of continuous machinery of clean surface.

This means for not only being used as organic Er Evil compounds and pollute, and be used as mercury, cadmium and the plumbous solid (for example refuse incinerator flying dust) that is polluted that is harmful to inorganic compound, only need a kind of method (being the reduce deposition of reducible compound described in the present invention) to handle.Rely on the method, can in a treatment step, solve two problems.

According to principle of the present invention, if described heavy metal exists in liquid, liquid rubbish or mud, mud, deposit and analog as pollutant, also can be by reducing metal with its being completely fixed.For fear of reoxidizing of the heavy metal of fine dispersion, must take other measures to avoid it again by liquidation.For contaminated soil or deposit, this can disperse chemical reaction (DCR) body to realize by for example being formed for the soil packing hydrophobic that discarded or technology in closed container or soil by machines utilize again.The the 849th to 929 page of " remedial works of contaminated soil " (RemediationEngineering of Contaminated Soils) that more detailed information was published in 2000 referring to works such as D.L.Wise, New York MarcelDekker.

Can remove heavy metal in the waste water fully by the reduce deposition on the aluminium of fine dispersion, wherein use the Ultra-Terrax T25 that S 25 N-18G dispersal devices are housed to carry out high degree of agitation.Because aluminium neither ductile neither be hard and frangible, need the much longer time to realize that by removing established copper layer the continuous machinery on clean aluminium surface recovers, although above-mentioned copper layer is extremely thin, almost be invisible.Making us wide-eyed is, electronics effectively identical in the complex compound that quickens organic reducible compound forms can be shifted accelerator and be used for herein.Thus, can be in a few minutes only stir its aqueous solution under the Ultra-Turrax equipment copper form of tetramine complex compound (even with) is removed fully by using in the existence of fatty amine.Known amine can significantly be coated on the metal surface, and this may to be electronics shift to accelerate and replace the easier reason of copper layer from the reducing metal surface.Same principle (being the buttressing effect of amine to the reduce deposition of heavy metal) also can be used for the quick immobilization of heavy metal of the material (particularly solid refuse, contaminated soil and analog) of any other kind.

If reducible compound is present in industrial refuse, residue, the accessory substance as pollutant, and in the material of the material of soil or similar soil, mud, mineral oil and similar mineral oil, no matter whether it wets, no matter also whether it has field trash, can not to this type of not homogeneous system directly carry out chemical treatment according to the present invention.But described contaminated materials will become manageable material after handling in the DCR reaction that has or do not have extra drying steps.Through the DCR treatment step, all described materials all are converted into dry powder, and can with any undesirable impurity in be separated by sieving.The the 849th to 929 page of " remedial works of contaminated soil " (RemediationEngineering of Contaminated Soils) that published in 2000 referring to works such as for example D.L.Wise, New York Marcel Dekker about the detailed description of DCR technology.

The pulverulent material that is obtained by the DCR step may also contain some moisture, therefore must be dried before with alkali metal treated.

Since described preferred implementation of the present invention in detail,, obviously can carry out various changes and change and do not depart from basic conception of the present invention for the personnel that are familiar with correlation technique.Thus, for example, although comprised the small amount of sample of laboratory scale mixing/grinding/pulverizing/dispersing apparatus and contaminated material and reagent in above-mentioned each example, obviously, for skilled receiver, obviously, the method that has comprised the continuous mechanical former bit recovery in metal surface of the reduce deposition that is used for reducible organic matter or inorganic matter, can suitably be revised and be used more on a large scale, thereby made that being used for detoxifcation industrial purposes, viable commercial and immobilization or other reproducibility methods becomes possibility.All these type of changes and change all are regarded as being within the definite in the above description scope of the present invention of its essence.In addition, the purpose that previous example is provided is to set forth specific implementation of the present invention, rather than is intended to limit the scope of method of the present invention.

Embodiment

Embodiment 1: remove TCB from liquid solution

The sodium (stoichiometric amount+10%) that 300mg is diced adds among the TCB of the 362mg (2mmol) in the 50ml cyclohexane that is contained in the there-necked flask (this there-necked flask is equipped with the IKA Ultra-Turrax T25 that has S 25 N-18G dispersal devices), and at room temperature the rotating speed with 11000rpm stirred 8 minutes under nitrogen.Sodium surface with metallic luster becomes light gray.Solid phase is taken out the colourless liquid sample after separating automatically.This sample does not contain the TCB or two of the amount that GC can detect-or list-chlorobenzene.

Embodiment 2:

The TCB of same amount reacts as the 300mg sodium on the aluminium powder of metallicity carrier with 150mg in an identical manner, and TCB was removed in 3 minutes fully.Sodium on the aluminium uses Retsch planetary type ball-milling S1 to grind in having the 50ml steel grinding pot of 3 steel balls with the mixture of two kinds of components of 2: 1 and 0.5% octadecylamine and made in 15 minutes.In the glove box under the nitrogen, open grinding pot and take out the reagent part.

Embodiment 3

In the presence of the 70mg n-butylamine, repeat the process of embodiment 2.Colourless liquid phase during the beginning of suspension in seconds becomes brownish red, seems more violent by adding the amine reaction, and its reason is that amine shifts the ability of accelerator and ability and the strong coating characteristic that causes thus as electronics.

With contain respectively the solid residue of residual sodium and aluminium and reduce deposition but not the TCB of dechlorination carry out reaction with methyl alcohol together, thereby generate the hydrocarbon of corresponding dehalogenation.Obtained same result by after finishing fully in the generation of the complex compound between TCB and the sodium described methyl alcohol being added former suspension.

Embodiment 4: the reductive dehalogenation of the TCB in the solid matrix

500mg sodium (stoichiometric amount+about 20%) is added in the homogeneous mixture of 554mg (3mmol) TCB in the solid (Millisil W8) of the similar soil of 100g, and grind using Retsch planetary type ball-milling S1 at room temperature having in the 500ml steel ball grinder of 4 steel balls in the presence of 0.5% octadecylamine.Grind after 30 minutes and jar is opened for the control purpose.The shallow sand of mixture has become light gray during beginning.Continue to grind after 30 minutes, color becomes grey black.Because the mixture after grinding is warmed up to about 80 ℃ rapidly after in being exposed to air, must in nitrogen, open jar and sampling must be carried out under nitrogen to avoid any volatilization of TCB or part dehalogenation product.

In second step, with whole mixtures 1/10th be equipped with magnetic stirrer and reflux condensing tube there-necked flask under nitrogen in cooling bath with the reaction of excessive slightly methyl alcohol, thereby produce the hydrocarbon of corresponding reductive dehalogenation.After using the Soxhelt extractor to extract the mixture that obtains with pentane, to the GC of colourless solution the analysis showed that do not have can detected amount TCB or any other organic halogen contained compound.

Embodiment 5: the reduction immobilization of copper

Ammoniacal liquor is added the aqueous solution of the about gram copper acetate of 100ml to form navy blue tetramine complex compound.Excessive slightly aluminium powder and a small amount of n-butylamine are added together.Ultra-Turrax with above explanation stirs with the suspension that obtains.Dark blue color disappeared in a few minutes, showed that copper ion is reduced to elemental copper fully.Solid separates after closing Ultra-Turrax automatically.Aluminium shows the gloss of copper.The comparative sample of handling in the same manner but not adding amine has kept its navy blue.

Claims (30)

1. carry out the method for reduce deposition with reducing metal to a kind of reducible compound itself or as the reducible compound of the form of the component part of mixture or solution, it is characterized in that at room temperature reducible compound being reduced continuously on the clean surface of the former bit recovery of continuous machinery of the reducing metal that is fixed on fine dispersion.

2. according to the method for claim 1, wherein reducible compound is a kind of organic compound itself or as the organic compound of the component part of solid or liquid mixture or solution, this reducible compound is reduced on the clean surface of the former bit recovery of continuous machinery that is fixed on reducing metal by generating complex compound.

3. according to the method for claim 1 or 2, wherein reducible organic compound is unsaturated aliphatic or alicyclic compound, aromatic, halide, aldehydes or ketones, nitro compound, and its form is itself or has derivative or solid or the liquid mixture or the solution of other functional groups.

4. according to the process of claim 1 wherein that reducing metal is lithium, sodium, potassium, magnesium, calcium, aluminium or iron, its form be itself or its physical mixture or its alloy or with the mixture of other metals or alloy or with the mixture of chemical inertness compound.

5. according to the method for claim 1 or 4, wherein chemical inert material is active carbon, graphite, powdery or ball shape plastics.

6. according to claim 1,4 or 5 method, wherein reducing metal and chemical inert material are fully ground together, thereby obtain as the homodisperse reducing metal on the chemical inert material of carrier.

7. according to the method for claim 1 or 4, wherein one of reducing metal is fully ground with another kind of powdery reducing metal.

8. according to claim 1,4 or 7 method, wherein lithium, sodium or potassium are fully ground with powdery aluminium or iron.

9. according to each method in claim 1 and 4 to 8, wherein reducing metal or the preparation that contains reducing metal are wrapped up by the interim inhibition coating of one deck.

10. according to the process of claim 1 wherein that the former bit recovery of continuous machinery of clean surface of reducing metal is that the effect of the shearing force by homogenizer or mixer or agitator or mechanical dispersion equipment, stamping machine, horizontal or vertical ball mill, vibrator, cutting type grinding mill, impact mill, extruder or kneader realizes.

11. method according to claim 1 to 10, wherein complex compound and any excessive reducing metal be made up of reducing metal and reducible organic compound in liquid phase are passed through decant, centrifugal or isolated by filtration together, so that carry out separate and reaction hydrogen or carbon source material subsequently.

12., wherein the complex compound and any excessive reducing metal that are made of reducible organic compound and reducing metal in solid system are reacted with hydrogen or carbon source material in the reaction that separates subsequently together according to the method for claim 1 to 10.

13. method according to claim 1 to 12, wherein being used for hydrogen or the carbon source material with the reaction complex compound that is made of reducing metal and reducible organic compound subsequently is water, aliphatic or alicyclic alcohol, phenol, amine, and its form is itself or contains derivative or its mixture of other functional groups; Halogenated organic, aldehyde, ketone or carbon dioxide.

14. according to one method in the above claim, wherein being reflected in the mixing of the chemical fixationization of having carried out reducible organic compound before this or milling apparatus of the complex compound of reducing metal subsequently and reducible organic compound carried out, and also can carry out in the mixing of a series connection that separates or milling apparatus.

15. according to one method in the above claim, the solid and the reducing metal that wherein will contain reducible compound grind in the presence of grinding aid.

16. according to the method for claim 15, wherein grinding aid is long-chain amine, polyvinylamine or polymine.

17. according to one method in the above claim, the solid that wherein will contain reducible organic compound grinds with reducing metal in the presence of inert organic solvents.

18. according to the method for claim 17, wherein inert organic solvents is biodegradable organic solvent, powdered plastic or active carbon.

19. according to one method in the above claim, wherein will contain solid preliminary treatment in a violent mixing or milling apparatus of the reducible organic compound of sneaking into, but so that increase the contact of reducible organic compound by the granularity that reduces solid particle.

20. according to claim 17,18 and 19 method, wherein preliminary treatment is carried out in the presence of grinding aid, organic solvent or its mixture.

21. according to the process of claim 1 wherein being formed on fatty amine, containing the organic polymer of uncle and/or the second month in a season and/or uncle's amino group or be the existence generation down of the saturated alicyclic compound of heteroatom of complex compound with nitrogen less than stoichiometric amount.

22. method according to claim 1, wherein reducible compound is an inorganic compound, its form be itself or as the part of solid or liquid mixture or solution, this inorganic compound is reduced on the clean surface of the former bit recovery of continuous mechanical type that is immobilized in reducing metal in the mode that coats.

23. according to each method in the above claim, wherein inorganic compound is the salt or the complex compound of heavy metal.

24. according to each method in the above claim, wherein will be converted into its undissolved metallic state by the reduction immobilization on the clean surface of the former bit recovery of continuous mechanical type of reducing metal as the heavy metal ion of the pollutant in the liquid phase, and thus electronics shift accelerator in the presence of make it from described liquid phase and remove fully by the abundant mixing of using high speed dispersing device.

25. according to each method in the above claim, wherein will be converted into its undissolved metallic state by the reduction immobilization on the clean surface of the former bit recovery of continuous mechanical type of reducing metal as the heavy metal ion of the pollutant in the solid, and thus electronics shift accelerator in the presence of pass through abundant mixing, grind, pulverize and in described solid being completely fixed.

26. according to the method for claim 24 or 25, wherein electronics transfer accelerator is an amine.

27. according to claim 24,25 or 26 method, wherein at heavy metal after the lip-deep reduce deposition of reducing metal is finished, add extra precipitating reagent and fully mix, grind, roll, with stop described heavy metal by reoxidizing mobilization again.

28. according to the method for claim 27, the sulfide that wherein said precipitating reagent produces for the in-situ reducing of the elementary sulfur by extra adding, above-mentioned elementary sulfur reacts in the process of fully mixing, grind, rolling with excessive reducing metal.

29. detoxifcation and process for fixation as the reducible organic and inorganic hazardous compound of the pollutant in material, mud, mineral oil and the similar mineral oil of industrial refuse, residue, byproduct and contaminated soil and similar soil, it is characterized in that do not carry out under the pretreated situation or through the DCR reaction treatment and, if necessary, carry out after extra heat and the chemical seasoning processing described contaminated material being handled according to one method in the above claim.

30. method according to claim 29, the exotic if wherein described contaminated materials has mixed, with its reaction in the DCR reaction, the classification of sieving subsequently, in process or under the situation of extra drying steps, one method during the uniform tiny screening thing that obtains required according to aforesaid right is handled, with reducible organic and inorganic noxious pollutant detoxifcation and immobilization.