CN107573084A

CN107573084A - A kind of method for handling discarded magchrome refractory flotation tailings

Info

Publication number: CN107573084A
Application number: CN201710818658.7A
Authority: CN
Inventors: 焦芬; 覃文庆; 刘维; 薛凯; 徐探
Original assignee: 中南大学
Priority date: 2017-09-12
Filing date: 2017-09-12
Publication date: 2018-01-12

Abstract

The invention discloses a kind of method for handling discarded magchrome refractory flotation tailings, it comprises the following steps：1) discarded magchrome refractory flotation tailings powder is prepared；2) acid treatment is carried out to the tailings powder in step 1)；3) chlorinating agent and carbonaceous reducing agent are prepared；4) tailings of acid treatment, chlorinating agent and carbonaceous reducing agent are mixed, it is and uniform by ground and mixed, then put it into the tube type resistance furnace under air atmosphere, and the blast pipe of tube furnace is passed through in the Drexel bottle containing sodium hydroxide solution, then it is being calcined, the volatile matter of roasting is being reclaimed by Drexel bottle, after the completion of roasting, remaining tailings is taken out and cooled down, the regenerative raw materials as refractory material.The method of the present invention is simple, efficiently separates and has reclaimed arsenic and antimony, realize the recycling to refractory material, it is therefore prevented that influence of the discharge of arsenic and its compound, chromium and compound and antimony and its compound etc. to environment, economy and obvious environment benefit.

Description

A kind of method for handling discarded magchrome refractory flotation tailings

Technical field

The invention belongs to the refractory material comprehensive reutilization field in non-ferrous metal metallurgy, and in particular to one kind processing is useless The method for abandoning magchrome refractory flotation tailings.

Background technology

The features such as magnesite-chrome brick has high temperature resistant, and intensity is big, and thermal shock resistance is excellent, and alkali resistance scouring is strong, becomes The most frequently used refractory material of non-ferrous metal metallurgy industry.During nonferrous metallurgy pyrometallurgical smelting, SO is produced₂Gas is more, stove It is interior to be in acidic atmosphere, metal bath good fluidity, furnace lining is easily corroded, destroy the performance of refractory material, thus China is annual Producing discarded magnesium brick has nearly 3,000,000 tons.

At present, to discard magchrome refractory processing mode mainly by melting or floatation recovery wherein content compared with High valuable metal, concentration landfill disposal then is carried out to it, although so simple processing mode cost is smaller, but made Into the wasting of resources, more importantly discard magchrome refractory and contain arsenic and its compound, chromium and compound and antimony and its change The noxious materials such as compound, great destruction can be caused to environment.Moreover, the raw material of magnesite-chrome brick production at present is at full stretch, especially It is high-grade chromite, thus how to recycle magchrome refractory is a urgent problem to be solved.

After discarded magchrome refractory reclaims main valuable metal by flotation, MgO, Cr in its flotation tailings₂O₃、 SiO₂、CaO、FeO、Al₂O₃Deng can meet production requirement, but still contain a small amount of arsenic and antimony in tailings.The presence of arsenic and antimony Tailings can be made to recycle brickmaking to be again severely impacted, be on the one hand due to arsenic and its compound, antimony and its compound it is molten Point and boiling point are relatively low compared with refractory material, during refractory material produces, can make to cause hole inside refractory material, shadow Ring the performance of refractory material；On the other hand, arsenic and its oxide have certain toxicity, on fireproof material production line, if there is arsenic Volatilization, it will have a strong impact on environment, influence whole production line.

The content of the invention

It is an object of the invention to provide a kind of method for handling discarded magchrome refractory flotation tailings, recovery can be efficiently separated Arsenic and antimony, realize the recycling of waste refractory materials.

The method that the present invention provides the discarded magchrome refractory flotation tailings of this processing, comprises the following steps：

1) magchrome refractory tailings after flotation is filtered by vacuum and dried, it is then uniform by grinding distribution, obtain Tailings powder；

2) diluted acid is sprayed on the powder tailings in step 1), soaks sample, and acid solution is filled with tailings by stirring Tap is touched, and is then stood, tailings is fully reacted with acid solution；

3) prepare chlorinating agent and carbonaceous reducing agent, and carbonaceous reducing agent is ground；

4) tailings of acid treatment in step 2) is mixed with the chlorinating agent in step 3) and carbonaceous reducing agent, and passed through Ground and mixed is uniform, then puts it into the tube type resistance furnace under air atmosphere, and by the blast pipe of tube furnace be passed through containing In the Drexel bottle of sodium hydroxide solution, then it is being calcined, the volatile matter of roasting is reclaimed by Drexel bottle, after the completion of roasting, Remaining tailings is taken out and cooled down, the regenerative raw materials as refractory material.

In the step 1), drying temperature should be less than 80 DEG C；Tailings powder 85-90% grain diameter is less than 0.074mm.

In the step 2), diluted acid used be watery hydrochloric acid and dilute sulfuric acid in one kind, dilute acid concentration 4-6mol/L；Tail The percentage by weight of slag and dilute acid soln is 20:(0.8-1.2), time of repose 10-12h.

In the step 3), carbonaceous reducing agent is the one or more in carbon dust, coke blacking, graphite powder；Milling time is 0.5-1min；The particle diameter of carbonaceous reducing agent after grinding should be less than 0.15mm；Chlorinating agent is magnesium chloride.

In the step 4), the mass percent of acid treatment tailings, magnesium chloride and carbonaceous reducing agent is 10:(0.5-1): (1.3-1.6)；Sintering temperature is 1000-1200 DEG C, roasting time 0.8-1h.

The principle of the present invention：

In discarded magchrome refractory, the content of arsenic and antimony is relatively low, it is difficult to separates.Wherein arsenic more than 90% is with calcium arsenate Form exist, the fusing point of calcium arsenate is up to 1455 DEG C, and most of arsenic is all wrapped up by refractory material other compositions, thus this Part arsenic is relatively stable, and in high temperature, 1,000 degree or so can not volatilize；But in the presence of reducing agent carbon, calcium arsenate is 1,000 Degree left and right can combustion decomposition product be arsenic oxide arsenoxide and calcium oxide, arsenic oxide arsenoxide can be reduced further into arsenic in reducing atmosphere, and arsenic It is readily volatilized in an environment of high temperature and its oxide boiling point is relatively low, thus easily separated under the high temperature conditions with refractory material.

Ca₃(AsO₄)₂+ C=3CaO+As₂O₃+CO₂

2As₂O₃+ 3C=4As+3CO₂

Antimony in the form of the oxide of antimony and antimony mainly to exist, and most of antimony is also all by refractory material other compositions bag Wrap up in, the boiling point of simple substance antimony is 1635 DEG C, and the oxide of antimony is mainly Sb₂O₃, boiling point is 1425 DEG C, and most of antimony is all resistance to Fiery material other compositions parcel, it is also highly stable at high temperature, but the hydrogen chloride that antimony and its oxide can generate with chlorinating agent Reacted at high temperature with chlorine, SbCl can be generated₃, only 222 DEG C of its boiling point is readily volatilized in an environment of high temperature, thus in height Easily separated under the conditions of temperature with refractory material.

2Sb+3Cl₂=2SbCl₃

Sb₂O₃+ 6HCl=2SbCl₃+3H₂O

The present invention discharges the compound for the arsenic and antimony being wrapped by by carrying out acid treatment to flotation tailings, Ran Houtong Reduction and chlorination processing are crossed, the existence form of arsenic and antimony is converted to the volatile state of high temperature by high temperature difficulty volatileness, so as to It is effectively separated from tailings, and reclaimed by alkali.

The beneficial effects of the invention are as follows：The method of the present invention is simple, efficiently separates and has reclaimed arsenic and antimony, realizes to fire resisting The recycling of material, it is therefore prevented that influence of the discharge of arsenic and its compound and compound of antimony etc. to environment, economy and Environmental Effect It is beneficial notable.

Brief description of the drawings

Fig. 1 is the process chart of the present invention.

Embodiment

For a further understanding of the present invention, the solution of the present invention is specifically described with reference to example, but should Understand, these descriptions are simply the further explanation present invention, rather than limitation of the present invention.

Embodiment 1

The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery silver smelting furnace, by flotation stream Flotation tailings after Cheng Huishou major metals, containing As it is 0.54%, Sb 3.13% in the tailings.

Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 80 DEG C Dry, obtained drying tailings grinds 20min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.Configuration concentration is 5mol/L watery hydrochloric acid, according to percentage by weight is 20 by tailings and dilute acid soln:1 mixing is equal It is even, time of repose 12h.

Coarse grained reducing agent coke powder is ground into 0.5min with vibrating ball-mill, its particle diameter is less than 0.15mm.By acid treatment Tailings, coke powder and magnesium chloride are 10 in mass ratio:0.5:1.5 ratio dispensing, is then ground.Material is laid in corundum On Noah's ark；And corundum Noah's ark is put into tube type resistance furnace, open air pump and be passed through air, blast pipe insertion is contained into sodium hydroxide The Drexel bottle of solution；Sintering temperature is set as 1200 DEG C, starting switch starts to be calcined, while timing；Stop heating after 0.8h, Room temperature is cooled to, filters and is precipitated in Drexel bottle, is reclaimed as metal fine fodder, takes out roasting residue, and carry out sampling analysis.

0.01%, Sb constituent contents are down to by chemically examining As constituent contents in residue and are down to 0.05%, substantially by arsenic and antimony Removing completely, this will not influence the regeneration technology of refractory material completely.

Embodiment 2

The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery plumbum smelting, by flotation stream Flotation tailings after Cheng Huishou major metals, containing As it is 0.95%, Sb 1.88% in the tailings.

Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 70 DEG C Dry, obtained drying tailings grinds 40min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.Configuration concentration is 6mol/L watery hydrochloric acid, according to percentage by weight is 20 by tailings and dilute acid soln:0.8 mixing Uniformly, time of repose 11h.

Coarse grained carbon powder of reducing agent is ground into 0.8min with vibrating ball-mill, its particle diameter is less than 0.15mm.By acid treatment tail Slag, carbon dust and magnesium chloride press 10:0.8:1.3 ratio dispensing, is then ground.Material is laid on corundum Noah's ark；And Corundum Noah's ark is put into tube type resistance furnace, air pump is opened and is passed through air, blast pipe is inserted into washing containing sodium hydroxide solution Gas cylinder；Sintering temperature is set as 1100 DEG C, starting switch starts to be calcined, while timing；Stop heating after 0.9h, be cooled to Room temperature, filter and precipitated in Drexel bottle, reclaimed as metal fine fodder, take out roasting residue, and carry out sampling analysis.

0.02%, Sb constituent contents are down to by chemically examining As constituent contents in residue and are down to 0.06%, substantially by arsenic and antimony Removing completely, this will not influence the regeneration technology of refractory material completely.

Embodiment 3

The raw material of use are discarded furnace lining-magnesium chromium firebricks of Hunan lead smeltery plumbum smelting, by flotation stream Flotation tailings after Cheng Huishou major metals, containing As it is 0.75%, Sb 1.38% in the tailings.

Take the flotation tailings, after vacuum filter filters, be placed in electric drying oven with forced convection and dried at 60 DEG C Dry, obtained drying tailings grinds 40min in agate grinder, it is uniformly dispersed and makes its 85-90% grain diameter Less than 0.074mm.Configuration concentration is 4mol/L dilute sulfuric acids, according to percentage by weight is 20 by tailings and dilute acid soln:1.2 mixing Uniformly, time of repose 10h.

Coarse grained reducing agent graphite powder is ground into 1min with vibrating ball-mill, its particle diameter is less than 0.15mm.By acid treatment tail Slag, graphite powder and magnesium chloride press 10:1:1.6 ratio dispensing, is then ground.Material is laid on corundum Noah's ark；And Corundum Noah's ark is put into tube type resistance furnace, air pump is opened and is passed through air, blast pipe is inserted into washing containing sodium hydroxide solution Gas cylinder；Sintering temperature is set as 1000 DEG C, starting switch starts to be calcined, while timing；Stop heating after 1h, be cooled to room Temperature, filter and precipitated in Drexel bottle, reclaimed as metal fine fodder, take out roasting residue, and carry out sampling analysis.

0.01%, Sb constituent contents are down to by chemically examining As constituent contents in residue and are down to 0.03%, substantially by arsenic and antimony Removing completely, this will not influence the regeneration technology of refractory material completely.

Claims

1. a kind of method for handling discarded magchrome refractory flotation tailings, comprises the following steps：

2) diluted acid is sprayed on the powder tailings in step 1), soaks sample, and acid solution is fully connect with tailings by stirring Touch, then stand, tailings is fully reacted with acid solution；

4) tailings of acid treatment in step 2) is mixed with the chlorinating agent in step 3) and carbonaceous reducing agent, and passes through grinding It is well mixed, then put it into the tube type resistance furnace under air atmosphere, and the blast pipe of tube furnace is passed through containing hydrogen-oxygen In the Drexel bottle for changing sodium solution, then it is being calcined, the volatile matter of roasting is reclaimed by Drexel bottle, will be residual after the completion of roasting Remaining tailings takes out cooling, the regenerative raw materials as refractory material.

2. a kind of method for handling discarded magchrome refractory flotation tailings as claimed in claim 1, it is characterised in that described In step 1), drying temperature should be less than 80 DEG C.

A kind of 3. method for handling discarded magchrome refractory flotation tailings as claimed in claim 1 or 2, it is characterised in that In the step 1), tailings powder 85-90% grain diameter is less than 0.074mm.

4. a kind of method for handling discarded magchrome refractory flotation tailings as claimed in claim 1, it is characterised in that described In step 2), diluted acid used is one kind in watery hydrochloric acid and dilute sulfuric acid；Dilute acid concentration is 4-6mol/L.

5. the method that magchrome refractory flotation tailings is discarded in a kind of processing as described in claim 1 or 4, it is characterised in that In the step 2), the percentage by weight of tailings and dilute acid soln is 20:(0.8-1.2)；Time of repose is 10-12h.

6. a kind of method for handling discarded magchrome refractory flotation tailings as claimed in claim 1, it is characterised in that described In step 3), carbonaceous reducing agent is the one or more in carbon dust, coke blacking, graphite powder；Milling time is 0.5-1min；Grinding The particle diameter of carbonaceous reducing agent afterwards should be less than 0.15mm.

7. the method that magchrome refractory flotation tailings is discarded in a kind of processing as described in claim 1 or 6, it is characterised in that In the step 3), chlorinating agent is magnesium chloride.

8. a kind of method for handling discarded magchrome refractory flotation tailings as claimed in claim 1, it is characterised in that described In step 4), the mass percent of acid treatment tailings, magnesium chloride and carbonaceous reducing agent is 10:(0.5-1):(1.3-1.6).

9. a kind of method for handling discarded magchrome refractory flotation tailings as claimed in claim 1, it is characterised in that described In step 4), sintering temperature is 1000-1200 DEG C, roasting time 0.8-1h.