CN107109526A

CN107109526A - Industrial processing method and its application to contain asbestos product

Info

Publication number: CN107109526A
Application number: CN201580053832.2A
Authority: CN
Inventors: 崔树青; 康雄; 康一雄; 埃里克·何岸; 阿兰·葛楠
Original assignee: Lake Gray Tech Investment Co
Current assignee: Lake Gray Tech Investment Co
Priority date: 2014-10-02
Filing date: 2015-10-01
Publication date: 2017-08-29
Also published as: WO2016051098A1

Abstract

The present invention relates to a kind of method for handling and including asbestos product, comprise the following steps：A) the comminuted solids product for including asbestos is provided, b) reactant mixture of the comminuted solids product comprising asbestos and inorganic acid aqueous solution is prepared, c) the comminuted solids product comprising asbestos is leached using inorganic acid aqueous solution, separated with d) solid phase/liquid phase leachate, the solid that the liquid phase leachate and/or alkali process that then acid pH processing is obtained in step d) are obtained in step d).

Description

Industrial processing method and its application to contain asbestos product

Technical field

The present invention relates to a kind of industrial processing method to contain asbestos product and its application.

Background technology

The hydrosilicate of self-assembling formation during asbestos are various metamorphic rocks, industry is processed as by modes such as mechanically actuateds The general name of available mineral fibres.Asbestos can be divided into two types：Serpentine (containing crystal material, is commonly referred to as fire stons Cotton) with the amphibole (species that to be divided into five different：Anthophyllite, amosite, crocidolite, actinolite and the tremolite).Asbestos fibre has Standby very attractive physicochemical properties, such as high fire resistance, resistance to chemical attack and very strong anti-tractive force.In view of these are special Property, many polymer use asbestos as additive, to obtain the inorganic composite materials of special properties.

Asbestos fibre structure is easy to suck respiratory tract by human body and is fixed on lung.Taken as to silicon and magnesium atom Generation, iron tramp is widely present among asbestos crystal.Doping iron can influence the stability of asbestos crystal, and then influence its toxicity And carcinogenicity.Asbestos are known from experience to people produces danger, has been considered as the immediate cause of celiothelioma and some pleural diseaseses.In 20 generation First three record in 10 years, the research progressively systematization of celiothelioma is suffered to asbestos industry workman.On asbestos processing and possible The limitation regulations worked in the environment of Asbestos-exposed are tentatively created in the 1970's.Between 1971 to 2000, exposed to stone The environment of cotton causes the growing number with Pleural Lesions to add after one times, therefore the nineties in last century, and western countries promulgate The use ban of asbestos, a large amount of asbestos are still sold in building materials form in Southeast Asia, South America and Eastern Europe.At present in the U.S. and Europe Continent, although the use of asbestos is strictly controlled, the situation exposed to asbestos still can be appeared in old building once in a while.

In China, especially in west areas such as Xinjiang, Qinghai, Gansu and Sichuan, asbestos harm problem grows in intensity.Five Over 10 years, the exploitation of asbestos mineral products causes the residual quantity containing asbestos product of these area accumulation very huge.Asbestos particles are very It is readily suspended in air and then propagates.In these areas, the asbestos waste that causes harm generally has comprising curling, soft The unique texture of superfine fibre.

The toxic chemical structure of asbestos, the method that can be separated by leaching with iron is destroyed, and is catalyzed carcinogenic freedom Base is converted into atoxic ferruginous deposits, and then releases or reduce its harm to environment and the mankind.Due to pollution problem, stone The comprehensive reutilization of cotton mine tailing is highly desirable to, in the case where adapting in the case of local economy sustainable development, takes into account local original Improve while the interests of material market and reply nature and living environment.

WO0017408 discloses a kind of method of use HCl treatment asbestos.The purpose of this request is isolated from serpentine Include the various materials of magnesium metal with reclaiming.But this part of file do not indicate how recycle asbestos tailings in other into Point, such as iron, nickel or the other valuable metals of cobalt.In addition, the method described by it is because the chemical raw material used and technique road The cost of line limits its application industrially.Patent US4110400 selections are after leaching 1.5-5 in pH using hydrogen sulfide Solution in precipitated impurities, such as cobalt and nickel non-ferrous metal.Sulfur dioxide be used to accelerate precipitation reaction, can be by processing time Less than one hour is foreshortened to, but these complicated gas-operateds industrially realize difficulty with larger.

Therefore, people are exploring the technique of more simple and inexpensive always, can quickly eliminate the adverse effect of asbestos, together When recycle its useful component.

In addition, traditional precipitation reaction between silicate and acid solution is known to be used in the preparation of silica, and then Novel polymer material with good dispersion and electrical resistance property is provided.The participation that they are constituted to material ensure that synthesis material Material possesses good characteristic, particularly the property in terms of mechanics, rheology and other dynamics.

The content of the invention

By long-term research, applicant develops one kind and uses extract technology, destroys asbestos chemical constitution and eliminates stone The method of the toxicity of cotton mine tailing.Most useful constituents can be recycled in asbestos tailings or discarded object.

Here it is why the application is related to a kind of method for handling and including asbestos product, it is characterised in that it includes following Step：

A) solid product containing asbestos that segmentation is crushed is provided,

B) prepare comprising the solid product crushed and the reactant mixture of inorganic acid aqueous solution,

C) comminuted solids are leached with inorganic acid aqueous solution,

D) solid phase/liquid phase separation,

Then on the one hand

E) by adding the acid pH leachate that alkaline reagent and oxidizer treatment are obtained in step d),

F) solid phase/liquid phase separation,

G) liquid that alkaline reagent processing is obtained in step f) is added,

H) solid phase/liquid phase separation, to obtain the sulfide of the hydroxide containing nickel and cobalt or nickel and cobalt in solid phase Mixture, may be selected to extract the mixture of nickel or cobalt or both, processing may be selected in magnesium salts in the liquid phase, is converted into magnesia.

And/or on the other hand

I) by the way that the solid obtained in step d) is mixed with the aqueous solution of alkaline reagent, a kind of reaction mixing is prepared Thing,

J) alkali process is carried out to the solid obtained in step d) by the aqueous solution of alkaline reagent,

K) solid phase/liquid phase separation,

L) made by adding the aqueous solution of ionic compound into the liquid obtained in step k) with obtaining a kind of solution For solion,

M) in step I) in obtain aqueous ionic solutions in add a kind of dilute solution, to obtain a kind of water of dilution Solution,

N) a kind of aqueous solution of mineral acid is added into the dilute aqueous solution obtained in step m), contains dioxy to obtain The sediment of SiClx, if it is desired to, it can be precipitated and be separated.

Therefore, method of the invention can not only eliminate the toxicity of asbestos, can also obtain value product, particularly Nickel, cobalt, the oxide and silica of magnesium or magnesium.

Therefore, processing method of the invention can comprise the following steps in the first embodiment：

A) solid product containing asbestos that segmentation is crushed is provided,

C) same cross is leached with inorganic acid aqueous solution to comminuted solids,

D) solid phase/liquid phase separation,

F) solid phase/liquid phase separation,

G) alkaline reagent processing is added) in the middle liquid obtained of step f),

H) solid phase/liquid phase separation, to obtain the sulfide of the hydroxide containing nickel and cobalt or nickel and cobalt in solid phase Mixture, may be selected to extract the mixture of nickel or cobalt or both, and magnesium salts in the liquid phase may be selected to be handled, and be converted into oxidation Magnesium.

According to the second embodiment of the present invention, the technique based on the present invention may comprise steps of：

A) solid product containing asbestos that segmentation is crushed is provided,

D) solid phase/liquid phase separation,

I) solid by will be obtained in step d) mixed with the aqueous solution of alkaline reagent, prepare a kind of reaction mixing Thing,

K) solid phase/liquid phase separation,

L) it is a kind of water-soluble to obtain by adding the aqueous solution of ionic compound into the liquid obtained in step k) Liquid, as solion,

According to the third embodiment of the invention, the technique based on the present invention may comprise steps of：

A) solid product containing asbestos that segmentation is crushed is provided,

D) solid phase/liquid phase separation,

F) solid phase/liquid phase separation,

K) solid phase/liquid phase separation,

Step a)

The solid product containing asbestos that segmentation is crushed can be, for example, drilling mud, coating, waterproof material, plasterboard Or gap filler, preferably fire proofing or plasterboard.After asbestos exploitation, tailing still includes asbestos component, and the tailing can preferentially be made The solid product containing asbestos crushed for the segmentation in the present invention.Here especially can be to exploit asbestos from Chinese Western Industry The residue obtained afterwards.

Solid product comprising asbestos can be by broken and grinding to increase its surface area, and this is conducive to Leach reaction.Powder The size of broken particle can for example be less than 149 microns, preferably less than 125 microns, especially less than 120 microns, especially About 74 micron levels obtained by dry type screening.

Therefore, people can use mineral crusher, the combination of multistage disintegrating process, such as first especially can be by Stage size reduction is to 150 microns, and second stage is crushed to 74 microns.

When the iron containing magnetic iron ore form in the solid product containing asbestos, people advantageously can be separated using magnetic separation Method handles pending product.Behind magnetic field, the iron content meeting in solid product containing asbestos used in present invention process Corresponding reduction, advantageously containing less than 6%, preferably less than 5%, especially less than 3%.

Step b)

The inorganic acid used in the aqueous solution for the solid product for containing asbestos for leaching process can be such as sulfuric acid, nitre Acid or hydrochloric acid, preferably sulfuric acid.

In reaction medium, the inorganic acid can be expressed as mass/volume, for example, from 1.102 to 1.260g/mL, preferably From 1.139 to 1.235g/mL, particularly from 1.155 to 1.219g/mL, especially about 1.178g/mL.

In the reaction medium obtained by step b), between the quality of solid product and the first inorganic acid aqueous solution volume Ratio be 0.1kg/L to 1kg/L, preferably 0.2kg/L to 0.7kg/L, particularly 0.23kg/L to 0.5kg/L, especially 0.25kg/L to 0.4kg/L.

The reaction medium obtained at the end of step b) preferably pH is less than 0.

Step c)

The leaching process for the aqueous solution for passing through inorganic acid to solid product is advantageously carried out in 70 DEG C to 110 DEG C of temperature, Carried out preferably between 79 DEG C to 103 DEG C, particularly carry out, especially enter between 89 to 95 DEG C between 84 to 99 DEG C OK.

The present invention is realized under the preferred conditions, and the comminuted solids product is handled with the aqueous solution of inorganic acid, is preferably made With sulfuric acid, liquid/solid ratio is such as 2.5 to 3.5L/kg, preferably from 2.7 to 3.3L/kg, particularly from 2.8 to 3.2L/kg, especially It is from 2.9 to 3.1L/kg.When acid used be sulfuric acid when, step b) acid consumption be expressed as during mass/volume ratio can be 15% to 35%, preferably from 20% to 32%, particularly from 22% to 30%, the reaction medium is most preferably from about 25%.

The time for carrying out leaching process to comminuted solids product by the aqueous solution of inorganic acid can be for example from 30 to 480 Minute, preferably from 40 to 240 minutes, particularly from 50 to 180 minutes, especially from 60 to 150 minutes.

When other implementation conditions of the invention are optimum condition, the leaching process to comminuted solids product is continuously being reacted Realized in device.For example, in first reactor, inserting newly broken solid product and carrying out Leach reaction, then in the second reaction The solid product leached in previous reactor is embedded in device, then with acid solution mixing.Acid solution in second reactor is excellent Select the acid solution of same nature in the first leaching reactor.After solid/liquid separation, liquid can be introduced in the first reactor and use In the leaching of comminuted solids product.In practice, it is preferable to realize the series connection of 2 to 6 reactors.

At this point in the reaction, the time of leaching process can be, such as 30 minutes to 4 hours, preferably from 40 to 120 Minute, particularly 50 to 100 minutes, especially from first reactor 60 to 90 minutes, and in second reactor leaching process Time can be such as 20 minutes to 480 minutes, preferably from 20 minutes to 120 minutes, particularly 20 to 90 minutes, especially From 20 to 60 minutes.Extraction time can be reduced by installing multiple reactors.At the end of leaching, the matter of acid solution, such as sulfuric acid Amount/volume ratio is preferably 5 to 80g/L, particularly from about 40g/L.

In order to obtain good leaching, the container is advantageously provided with agitator, especially radially and axial agitator.

Step d)

Solid/liquid separation step d) after leaching can use such as vacuum filter, centrifugal rotation drier or pressure mistake Filter, preferably rotary dryer or filter-press, especially filter-press.The separating step allows on the one hand to be wrapped Containing the solid mixture based on iron and silicon, the compound solution for including and can be directly used for next step is on the other hand obtained.

The pH that this solution preferably has is about 0.

Step e)

In the alternative techniques of the inventive method, the solution (leachate) obtained in step d can be carried out in step e PH is the processing of acid condition, adds alkaline reagent and oxidant into the solution in this step.

It should be noted that in this application, usual indefinite article " one " should be considered as a general plural number (meaning For " at least one " or " one or more "), unless otherwise indicated by context (1 or " solely a kind of ").Thus, for example, when its quilt It is designated as adding above-mentioned alkaline reagent, it is to add one or more alkaline reagents, is equally applicable for oxidant.

,, can be in such as pH by 0 to 4 using alkaline reagent and oxidant under condition of acidic pH in process step e) Under conditions of carry out, preferred pH is that, more preferably by 2 to 4,2.5 to 3.5, especially about 2.5 are arrived in particular by 1 to 4 3。

Alkaline reagent is used in particular for controlling the pH in step e), to keep the pH value between 0 and 4.By the present patent application People preferentially proves, is possible by the way that pH is maintained at greater than or equal into 0 to precipitate Fe-base compound.When treatment conditions tool There is more acid pH value, when especially less than 0, the solubilization of iron compound can be caused so that it can not be from former medium Separation.Alkaline reagent used in the present invention is preferably the oxide or hydroxide of alkali metal or alkaline-earth metal, preferably oxygen Change magnesium, magnesium hydroxide, sodium hydroxide, calcium oxide, calcium carbonate, magnesium carbonate, sodium oxide molybdena or ammonia, particularly magnesia, calcium oxide, carbon Sour calcium or ammonia, especially magnesia, or their mixture.It will hereinafter show, the present invention is conducive to using magnesia The subsequent step of the technique of description.

Similarly, the inorganic acid as described in abovementioned steps b), can be used for the place of the pH in acidic aqueous solution in step e) Reason, to keep pH value between 0 and 4.Inorganic acid can be such as sulfuric acid, nitric acid or hydrochloric acid, preferably sulfuric acid.

Oxidant can improve the degree of oxidation of iron, and this is conducive to the oxidation state of relative cobalt and nickel selective precipitation iron.Alkali Property reagent and oxidant be applied in combination allow iron selective precipitation.Used oxidant can be, such as chlorine, peroxidating The gases such as hydrogen, nitrogen, sulfur dioxide or oxygen, preferably sulfur dioxide or oxygen and nitrogen, especially oxygen, or it is wherein several Mixture, the mixture of such as sulfur dioxide and oxygen.A part for the oxidant used, which may be constructed in previous steps, to be made Acid (if the acid is oxidizing acid), such as sulfuric acid.

Step f)

Solid phase/liquid phase separation step f) after this step e) allows to reclaim the iron and other heavy metals precipitated.It can To be carried out under the conditions of previously described solid phase/liquid phase separation step d) similar operations.On the one hand it allow the change of iron Compound is separated into solid phase, on the other hand can obtain the liquid phase for next step solution.

Step g)

Step g) is addition alkaline reagent to the operation in the liquid phase reclaimed from step f), to obtain more " meta-alkalescence " PH value, refer to relative to acid pH processing step e) in pH there is relatively low acidity.Especially, step g) is big in pH value Carried out under conditions of 4, to allow the selective precipitation containing cobalt or nickel compound.Preferably pH is 4 to 9.5, more preferably 7 To between 9.5, particularly 7.5 and 9.

It is preferred that keeping the pH in step g) to be less than or equal to 9.5.In fact, the applicant preferentially proves, it is high in pH When 9.5, what step f) was obtained be deposited in can include the magnesium compound in more solution containing cobalt or while nickel, so that It is no longer possible optionally to obtain these metals.

In implementation steps g) optimum condition, flocculant is added in solution after the reaction, preferably sulfur-containing compound, can To improve the precipitation of metal (cobalt and nickel).Sulphur compound can be such as alkali metal sulphide, such as vulcanized sodium or potassium sulfide, spy It is not vulcanized sodium.

It should be noted that if selection addition flocculant helps the precipitation of nickel, step g) is advantageously in pH between 5 to 6 Between carry out, can be realized by adding such as magnesia.

If selecting vulcanized sodium as flocculant, the ratio of vulcanized sodium and the solid containing asbestos can be 0.4% to 0.8%, excellent Selection of land is from 0.5% to 0.7%, particularly from about 0.6%.

If selecting vulcanized sodium coprecipitated nickel hydroxide, the precipitation is advantageously carried out at a temperature of 40 DEG C to 60 DEG C, preferably 45 DEG C To 55 DEG C, particularly from about 50 DEG C.

To this end it is possible to use, alkaline reagent same in such as abovementioned steps e), especially using magnesia, or itself and one kind Or the mixture of a variety of other alkaline reagents.Magnesia may come from, as being discussed immediately below, in method of the invention Subsequent step.

Step h)

Solid phase/liquid phase separation step h) after step g) allows to reclaim the precipitation containing cobalt and nickel compound.It can To be carried out under conditions of similar to step f) solid phases/liquid phase separation operation.It allows to separate the solid phase containing nickel and cobalt, wherein Metal exists in the form of its hydroxide, and obtains the solution for next step.

Nickeliferous and cobalt compound optionally can be handled to extract nickel and cobalt, lift its value.These processing It may include by adding alkaline reagent precipitation and separation, preferred as alkali or alkaline earth oxide, particularly magnesia.

Suitable processing can contain the solution of magnesium salts including the use of drier such as dense sulfuric acid treatment, to provide sulfuric acid Magnesium, can obtain the magnesia of solid forms by being heat-treated.

Advantageously, the step of method of the invention includes solid oxidation magnesium needed for obtaining, most preferably consolidated using this Body magnesia is used as the alkaline reagent used in such as step e) and step g).

Step i)

In the technique of the present invention, step d) or step h) can carry out subsequent treatment：By being obtained in blend step d) Solid and the aqueous solution of alkaline reagent prepare a kind of reaction medium.

In step i), the ratio between the quality of solid and the volume of the alkaline reagent aqueous solution that are obtained in step d) Rate is 0.4kg/L to 0.6kg/L, preferably from 0.44kg/L to 0.55kg/L, in particular from 0.47kg/L to 0.52kg/L, Especially about 0.5kg/L.

The present invention is implemented under optimum condition, and the alkali used is sodium hydroxide, the quality of the solid obtained in step d) and Ratio between the volume of the alkaline reagent aqueous solution in the reaction medium obtained in step e) is 0.4kg/L to 0.6kg/L, excellent Selection of land be from 0.44kg/L to 0.55kg/L, in particular from 0.47kg/L to 0.52kg/L, especially about 0.5kg/L.

Step J)

The solid obtained using the alkaline reagent aqueous solution to step d) carries out alkali process.React the temperature at 60 DEG C to 100 DEG C Advantageously carried out under degree, preferably from 70 DEG C to 90 DEG C, especially from 75 DEG C to 85 DEG C, especially about 80 DEG C.

Carrying out alkali process to the solid obtained in step d) using the alkaline reagent aqueous solution can be, such as 180 to 480 points Clock, preferably 240 to 420 minutes, especially about 300 minutes to 360 minutes in particular, 320 minutes.

Step k)

Solid phase/liquid phase separation step k) after this step j) can be in analogy previously described solid phase/liquid phase point Carried out under operating condition from step d).

The separating step allows on the one hand to obtain a kind of solid, on the other hand obtains the liquid available for next step.Should Liquid contains silicon compound, such as silicate.

Step l)

A kind of deionized water solution is added in the liquid obtained in step k), it is made up of the ion of electroneutral compound Solution.Under preferred conditions for implementing the invention, the ionic compound includes chemical combination contained by the liquid obtained in step k) Same ion in thing.Sodium sulphate, sodium chloride, potassium sulfate are preferably chosen from, more preferably sodium sulphate or sodium chloride, especially excellent Selection of land is sodium sulphate.For example, when the first inorganic acid is sulfuric acid, when alkaline reagent is sodium hydroxide, sodium sulphate is advantageously selected, because Include the former anion and cation simultaneously for it.

Sodium sulphate can advantageously come from the leachate obtained in step d).Thus, one kind, which is recycled, is achieved.

The aqueous solution of ionic compound is preferably saturation.

In implementation process under optimum condition of the present invention, for example the first inorganic acid is sulfuric acid, and the alkaline reagent is hydrogen Sodium oxide molybdena, when ionic compound used is sodium sulphate, the quality of the solid obtained in step d) and the addition in step l) Ionic compound saturated aqueous solution volume between ratio, can be from 1kg/L to 5kg/L, preferably from 15kg/L To 4.5kg/L, in particular from 1.7kg/L to 4.3kg/L, especially from 1.9kg/L to 4.1kg/L.

Step M)

A kind of dilute solution is added in the deionized water solution obtained by step l), a kind of aqueous solution of dilution is obtained.

The dilution preferably waterborne liquid used in the step of after, the preferably aqueous solution of such as sodium sulphate, water.

In the case where implementing other optimum conditions of the present invention, quality and step m) addition of the solid obtained in step d) Ratio between diluent liquid volume is 0.005kg/L to 0.4kg/L, preferably from 0.075kg/L to 0.3kg/L, especially From 0.09kg/L to 0.25kg/L, especially 0.01kg/L to 0.2kg/L.

It is alkaline in the pH of the obtained dilute aqueous solutions of step m), it is special preferably from 10 to 13.75 more than or equal to 7 Not from 11 to 13.5, especially 11.5 to 13.25.

Step n)

A kind of inorganic acid aqueous solution is added in the dilute aqueous solution that step m) is obtained can reduce the dilute aqueous solution PH value, and the precipitation silicon compound in the form of such as silica.

Step n) precipitation is that the aqueous solution for adding inorganic acid by the dilute aqueous solution obtained in step m) is carried out, to obtain Must be less than or equal to 9 pH, preferably less than 8, particularly less than 7, especially between 5 to 6.

The inorganic acid used in aqueous solution precipitated silica can be sour identical with described by above-mentioned steps b), for example Realized by sulfuric acid, nitric acid or hydrochloric acid, preferably sulfuric acid or hydrochloric acid, especially sulfuric acid.

Step n) be deposited in 80 DEG C to 100 DEG C at a temperature of advantageously carry out, preferably from 80 DEG C to 98 DEG C, particularly From 85 DEG C to 97 DEG C, especially from 88 DEG C to 95 DEG C.

Step n) duration can be for example from 20 to 80 minutes, preferably from 25 to 70 minutes, particularly from 30 Minute to 60 minutes, especially about 45 minutes.

Under preferred conditions for implementing the invention, the step n) is completed by continuously adding inorganic acid aqueous solution, is added Acid concentration is gradually reduced.

Under the conditions of particularly preferred in last of the invention embodiment, the first inorganic acid aqueous solution concentration be from 30% to 65% mass fraction, it is therefore preferable to 35% to 60%, in particular from 40% to 55%, the second inorganic acid aqueous solution is dense Spend for 5% to 20%, it is therefore preferable to 8% to 17%, in particular from 10% to 15%.

Under the optimum condition that the present invention is implemented, the first includes the aqueous solution quilt that mass fraction is 40% to 55% sulfuric acid It is added in the dilute aqueous solution obtained by step m), then the pH value to reduce the dilute aqueous solution adds to about 6 Containing second aqueous solution that mass fraction is 10% to 15% sulfuric acid, to reduce the pH value of the dilute aqueous solution to 5 to 6.

The inorganic acid aqueous solution that concentration is gradually decreased can allow for, and utilize the heat section sent of the acid/water reaction Energy is saved, and controls the form of sediment.

Advantageously, the sediment obtained in step n) can be obtained preferably by solid/liquid separation.

Solid phase/liquid phase separation operation after step n) can be similar to foregoing solid phase/liquid phase separation step d's) Under the conditions of carry out.

The separating step, it is allowed on the one hand obtain a kind of liquid, on the other hand obtain the titanium dioxide of Amorphous particles form Silicon, i.e., the nodeless mesh with Si atoms and O atom is periodically combined.

Preferably, a small amount of stabilizer is added, such as sodium chloride, stabilisation time of last silicate can remain 36 small When.

The method of the present invention can be realized by discontinuous flow, or preferably be realized by continuous stream.

Under the optimum condition that the present invention is implemented, the comminuted solids product comprising asbestos has the granularity of 200 to 400 mesh, Reacted in the aqueous sulfuric acid of 25% concentration, the ratio of acid solution/solid is 3L/kg, and filtrate is entered at a temperature of 80 DEG C to 100 DEG C OK, the oxidant includes oxygen.In such a process, it is preferable that leach and carried out in several separated reactors, especially Carried out preferably under this step above-mentioned condition.Even further preferably, may be selected in alkaline agent e) and g) used in step The magnesia obtained at the end of flow.

The technique of the present invention is highly useful.These techniques can be used for processing asbestos waste or asbestos tailings, while producing magnesium And other metals are such as cobalt, nickel, iron and its alloy.These techniques can be also used for the manufacture of silica.The nothing obtained The silica dioxide granule of setting, the diameter that its porosity is at least 50% is less than or equal to 40nm.Amorphous silica particles Porosity pass through Micromeritics Autopore porosity analysers measure.

These characteristics of the product can be obtained in experimental section as follows.They are demonstrated on the other hand Technique used in the present invention can be used for processing asbestos or asbestos tailing.Also confirm and obtained using by the method for the present invention simultaneously Amorphous silica particles, especially can be used as production single-crystalline-silicon solar-cell panel raw material sources.

Technique of the present invention can be implemented in commercial scale, i.e., at least daily 500 kilograms of asbestos wastes are handled, It is preferably at least daily 900 kilograms.

Here it is why herein described process can be used for, including

The going of-asbestos tailings or asbestos material residue does harm to and gone danger

Valuable part in-recovery asbestos tailing, to prepare foregoing magnesium and other metals

The manufacture of-support silicon-containing catalyst carrier

- the production available for relevant food additive

- it can be used for macromolecular compound, include the manufacture of the enhancer additives of rubber and plastic agent

The manufacture of-the non-crystalline silicon that can be used in solar panel production raw materials.

For realizing that the optimum condition of above-mentioned technique is also applied for reaction of the present invention for the purpose of other target products, this A little conditions can often obtain optimal recovery rate.

Embodiment

The following examples can be used for illustrating herein described technique.

Example

Common step

Crush and grind a kind of asbestos tailings bulk comprising magnetic iron ore, be 74 to 37 microns (respectively square to granularity - 200 mesh and -400 mesh that mesh screen is determined).After grinding, ratio of the iron in gained powder is 3%.

1st step

In first reactor, 65 grams of powder and aqueous sulfuric acid are mixed at high temperature, acid solution volume/solid masses Ratio is (R), and the time is (T), and temperature is (θ).Using contain sulfuric acid percentage by weight be P1 aqueous sulfuric acid.

Then filtered on buchner funnel is used, liquid phase L1 and solid phase S1 is obtained.Solid phase S1 includes silicon.

2nd step

Then liquid phase L1 is transferred to the reaction vessel of second equipment circulation pipe, the crystallizer possesses distributing damper. Sodium hydroxide is added under stirring into solution, oxygen is introduced, impeller is adjusted, pH maintains target position.Precipitated.

Using filtered on buchner funnel, liquid phase L2 and solid phase S2 are obtained.It is miscellaneous that solid phase S2 contains the iron existed with form of iron oxide Matter.

3rd step

Then liquid phase L2 is transferred in the 3rd reactor, the reactor has the type of crystallizer simultaneously, and is aided with and stirs Mix.Sodium hydroxide is added, the pH value in alkaline range, about 9 is obtained.Now produce sediment S3, the hydrogen-oxygen comprising nickel and cobalt Compound, and liquid phase L3, comprising magnesium salts, use filtered on buchner funnel.

4th step

L2 liquid phase dense sulfuric acid treatments, obtain hydrated sulfuric acid magnesium precipitate, and sulphur is calcined together, obtains magnesia.

The recovery rate of magnesium, iron, nickel and cobalt is determined.Recovery rate be expressed as relative to be present in containing asbestos rise The percentage of respective element total amount in beginning material.

Embodiment 1 to 6

The extraction result (%) obtained is as follows

Embodiment	Magnesium	Iron	Nickel	Cobalt
					1	84%	42%	75%	28%
2	80%	38%	71%	32%
					3	87%	56%	82%	45%
4	81%	51%	76%	35%
					5	75%	44%	71%	34%
6	41%	78%	24%	17%

The result of acquisition shows sulfuric acid mass fraction more than 30%, and the recovery rate of magnesium, nickel and cobalt falls sharply.Ratio shared by sulfuric acid It is lower, the recovery rate of three kinds of more excellent metals is resulted in especially with 26-28% sulfuric acid.

Embodiment 7 to 16

The extraction result (%) obtained is as follows

The result of acquisition shows that the recovery rate of magnesium, nickel and cobalt is more good at high temperature, is one particularly in extraction time Under conditions of hour.

Embodiment 17

1st step

In the reactor equipped with mechanical agitator, 64.51 grams of mixing containing the powder obtained in above-mentioned steps and 200mL aqueous sulfuric acids (mass fraction 25.5%).60 minutes, formation under so obtained reactant mixture is stirred at 80 DEG C Sediment.

Using the ZPG vacuum filters of Joyal Machinery companies, 54.37g solid phases S1A is obtained.

2nd step

Then solid phase S1A is transferred in second reactor, and mixed with 110mL sodium hydrate aqueous solutions (977g/L). So obtained reactant mixture is heated 90 minutes under agitation at 90 DEG C.

Then filtered using the ZPG vacuum filters of Joyal Machinery companies, obtain solid phase S2a, liquid phase L2a will It is directly used in next step.

3rd step

98mL liquid phases L2a is transferred in the 3rd reactor, and it is mixed with 27.2mL saturated aqueous sodium sulfates (300g/L) Close.Then it is diluted with water in the mixture, until volume is 680mL, the pH of the aqueous solution is 13.22.Add 21mL sulfuric acid water Solution (mass fraction 44%), so as to reduce the pH value of the aqueous solution to 9.63.

Adding the 3.2mL concentrated sulfuric acids (mass fraction 25%) reduces the pH value of the above-mentioned aqueous solution to 5.91.

Finally, the 0.7mL concentrated sulfuric acids (mass fraction 13.5%) are added, to reduce the pH value of the above-mentioned aqueous solution to 5.

After 45 minutes, the precipitation of silica of amorphous granular form is obtained, Joyal Machinery companies are used ZPG vacuum filters are separated.

Quality obtained by amorphous silicon di-oxide particle is 12.1g, is 59.8% of whole silicon in initial powder.

Embodiment 18

1st step

Powder and 349mL aqueous sulfuric acids (25% mass point that 129.7 grams of common steps are obtained are mixed in the reactor Number).So obtained reactant mixture is heated 120 minutes under agitation at 90 DEG C.

Then the isolated 110.3g solid phases S1b of ZPG vacuum filters of Joyal Machinery companies is used.

2nd step

48.6 grams of solid phase S1b are transferred in second reactor, and mixed with 100mL sodium hydroxide solution (200g/L) Close.So obtained reactant mixture is heated 90 minutes under agitation at 90 DEG C.

Then the isolated 24mL liquid phases L1b of ZPG vacuum filters of Joyal Machinery companies is used.

3rd step

Liquid phase L2b is subsequently transferred to the 3rd reactor, and is mixed with 12.5mL saturated aqueous sodium sulfates (300g/L).So The mixture is diluted by adding water afterwards, until volume is 303.7mL, the pH value in the aqueous solution is 11.59.

Then 7.0mL aqueous sulfuric acids (44% mass fraction) are added in the above-mentioned aqueous solution, so as to reduce described water-soluble The pH value of liquid is to 2.56.

Quality obtained by amorphous silicon di-oxide particle is 19.5g, is 96.0% of whole silicon in initial powder.

Claims

1. a kind of handle the method for including asbestos product, comprise the following steps：

A) the comminuted solids product for including asbestos is provided,

B) reactant mixture of the comminuted solids product comprising asbestos and inorganic acid aqueous solution is prepared,

C) the comminuted solids product comprising asbestos is leached using inorganic acid aqueous solution,

D) solid phase/liquid phase leachate separation,

Then on the one hand

F) solid phase/liquid phase separation,

H) solid phase/liquid phase separation, obtains the mixture of the sulfide of the hydroxide containing nickel and cobalt or nickel and cobalt in solid phase, The mixture of extraction nickel or cobalt or both may be selected, magnesium salts in the liquid phase may be selected to be handled, and be converted into magnesia.

And/or on the other hand

I) by the way that the solid obtained in step d is mixed with the aqueous solution of alkaline reagent, a kind of reactant mixture is prepared,

K) solid phase/liquid phase separation,

L) by adding the aqueous solution of ionic compound into the liquid obtained in step k), to obtain a kind of aqueous solution, make For solion,

M) in step I) in obtain aqueous ionic solutions in add a kind of dilute solution, to obtain a kind of the water-soluble of dilution Liquid,

N) a kind of aqueous solution of mineral acid is added into the dilute aqueous solution obtained in step m), contains silica to obtain Sediment, if it is desired to, can be precipitated and be separated.

2. technique according to claim 1, it is characterised in that step e) is to carry out between 0 to 4 in pH, preferably from 1 to 4, More preferably from 2 to 4, particularly from 2.5 to 3.5, especially from 2.5 to 3 or so.

3. technique according to claim 1 or claim 2, it is characterised in that step g) is carried out between pH is 4 to 9.5, preferably From 7 to 9.5, more preferably from 7.5 to 9.

4. the technique according to claims 1 to 3, it is characterised in that the inorganic acid is sulfuric acid, in step b) reaction medium In weight/volume be 22% to 30%.

5. the technique according to Claims 1-4, it is characterised in that comminuted solids product is handled with inorganic acid aqueous solution, 70 DEG C to carrying out at a temperature of 110 DEG C.

6. according to one of claim 1 to 5 technique, it is characterised in that in the leaching process comminuted solids product with Liquid/solid ratio in inorganic acid aqueous solution is 2.5L/kg to 3.5L/kg.

7. according to one of claim 1 to 6 technique, it is characterised in that the leaching process of comminuted solids product is multiple Realized in continuous reactor, new comminuted solids product is placed in first reactor, placed in second reactor Be the solid product leached in previous reactor, the solid product is mixed in the reactor with acid solution.

8. according to one of claim 1 to 7 technique, it is characterised in that step e) or step g) alkaline reagent can select The magnesia obtained from step h).

9. according to one of claim 1 to 8 technique, it is characterised in that the liquid obtained in step g) processing by step f), Use metallic compound flocculant, such as sulfide.

10. according to one of claim 1 to 9 technique, it is characterised in that the alkaline reagent in step i) is sodium hydroxide, The body of the solid masses obtained in step d) and the alkaline reagent aqueous solution in the second reaction medium obtained in step i) Ratio between product is 0.1kg/L to 1kg/L.

11. according to one of claim 1 to 10 technique, it is characterised in that the compound includes what is obtained by step k) Ion in liquid, and be sodium sulphate.

12. according to one of claim 1 to 11 technique, it is characterised in that step n) precipitation is by by described second Inorganic acid is added in the dilute aqueous solution that step m) is obtained, and is obtained until pH is less than or equal to 5.5.

13. the application of technique as described in one of claim 1 to 9, the technique includes step a) to h),

- it is used for going evilization and depolluting for asbestos tailings or asbestos waste

- it is used for the recycling of wherein valuable constituent, to prepare magnesium and other metals.

14. the application of technique as described in one of claim 1 to 7 and 10 to 12, the technique includes step a) to d) and i) extremely N),

- available for the manufacture for supporting silicon-containing catalyst carrier

- the production available for relevant food additive