CN1033280C

CN1033280C - Recovery method for smoke containing iron, manganese, zinc, lead and other elements

Info

Publication number: CN1033280C
Application number: CN93103927A
Authority: CN
Inventors: 李景捷; 李宏; 王万军; 洪从甲
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 1993-04-01
Filing date: 1993-04-01
Publication date: 1996-11-13
Anticipated expiration: 2013-04-01
Also published as: CN1093117A

Abstract

The present invention relates to a recovery method of smoke containing the elements of iron, manganese, zinc, lead, etc., which belongs to the technical fields of treating non-ore materials and producing non-ferrous metals and the compounds thereof. The smoke is immersed in alkali solution, and the zinc, the lead, etc. in the smoke are leached out and dissolved in the alkali solution; after solid-liquid separation, sodium sulfide is added to the leach liquor for generating the mixture of zinc sulfide and lead sulfide by stirring at room temperature, and the mixture is put in diluted hydrochloric acid (pH<5) for generating zinc chloride solution after the mixture is washed by water; then, the lead sulfide is separated by filtration, and the pH value of the zinc chloride solution is adjusted to the value from 5 to 6 for generating the precipitate of zinc oxide; the purity of the zinc oxide and lead monoxide is higher than 95 percent. The present invention has the advantages of simple equipment, low energy consumption, high yield and no pollution.

Description

Recovery method for smoke containing iron, manganese, zinc, lead and other elements

The invention belongs to material such as the waste material of handling non-ore, to produce non-ferrous metal or other compound.

In the flue dust that iron and steel enterprise and ferroalloy works produced, except iron, manganese, also have some Volatile Elements zinc, lead etc.This flue dust is one of public hazards of puzzlement enterprise, but the potential utility value is arranged also, for a long time, the existing method of this flue dust of much utilizing is come out, be broadly divided into following several: 1. medium temperature roast volatilization method: this flue dust is warming up to 1000 ℃ of left and right sides reducing roastings in rotary kiln one class reactor, makes zinc, plumbous evaporation, in gas phase, be reoxidised into zinc oxide, plumbous oxide, be condensed into small-particle, rely on complicated recovery system to collect the mixture of zinc oxide and plumbous oxide.2. gravity washing method of sieving: utilize the difference of each element compound particle, severe, diameter in the flue dust, gravity treatment is sieved in water, isolates main ferruginous breeze and mainly contains the breeze of zinc, lead.3. alkali soaks electrolytic process: place alkaline solution to leach this flue dust, treat zinc in the alkaline solution, when lead concentration is higher, distinguish electrowinning again, in these three kinds of methods, first method reclaims because of zinc oxide, particles of lead oxide are little not exclusively, power consumption is high, and can only collect the mixture of zinc oxide and plumbous oxide, can not directly be used; Second method is resulting all to be primary raw materials, also needs mainly to contain at the 1000 ℃ of left and right sides roasting temperatures breeze of zinc, lead, just can obtain the mixture of zinc oxide and plumbous oxide; When though the third method alkali soaks in the flue dust zinc, lead can leach more than 90%, and energy consumption is low, raw materials consumption is low, but to use chemical method to purify leach liquor before the electrolysis of back, handle complexity, current consumption is big during electrolysis, the cost height, and, and cause direct product metallic zinc and metallic lead can not form scale economics because of zinc in the flue dust of handling, lead concentration are not high.

The objective of the invention is, both made full use of the various resources in the flue dust, reduce running expense again, to obtain higher economic benefit, soon iron, manganese and zinc, lead separate as much as possible in the flue dust, and the technical pure product that adopts more economical method production directly to use again reduces production costs simultaneously.

Content of the present invention is, utilize alkali to soak the reasonable part of electrolytic process forward, alkali soaks flue dust, wherein zinc, lead etc. are leached in the alkaline solution, behind separating liquid and the solid, adopt chemical Treatment, directly extract zinc oxide and plumbous oxide, the existing CaO of the adding precipitator method are also adopted in the removal of Si and Al in the leaching circulating mother liquor, and treatment process is as follows:

In the leach liquor that contains zinc＜200mg/ml and lead＜200mg/ml, add by required alkalization sodium solid or the solution of stoichiometric calculation, make following reaction takes place in the solution:

Also can use the H that produces in the operation of back ₂S gas replaces Na ₂S carries out precipitin reaction:

After stirring 5～60 minutes under the room temperature, in static 2 hours, the mixture of filtering separation leach liquor and zinc sulphide, lead sulfide then.Return leaching process as mother liquor after the leach liquor adjustment, and zinc sulphide, lead sulfide are put into dilute hydrochloric acid solution after washing, keep pH＜5 of solution, be stirred to pH under the room temperature no longer to change, make zinc sulphide and hydrochloric acid reaction generation ZnCl ₂And dissolve.Refilter and separate lead sulfide and liquor zinci chloridi, transfer to 5～6 with the pH of liquor zinci chloridi is counter, make zinc wherein generate the zinc oxide precipitation, obtain solid oxidation zinc after filtration.Can make product after the oven dry of lead sulfide and zinc oxide and sell directly and use, zinc oxide and lead sulfide purity all＞95%, the H of zinc sulphide and hydrochloric acid reaction generation ₂S gas can be collected and be used for part replacement Na ₂S adds, with depositing zinc and lead.

When silicon in the leach liquor and aluminum concentration too high (during the content of silicon and aluminium 〉=0.05mg/e), the present invention can go in above-mentioned processing and convert milk of lime in the leach liquor or add fixedly lime, precipitation removes silicon and the aluminium in the alkaline solution, handle the content that obtains silicon and aluminium in the miscellany to reduce sulfide precipitation, the quality that is added to CaO in the alkaline solution is SiO in the alkaline solution ₂And Al ₂O ₃1～3 times of amount, 3 hours with interior silicon-dioxide and the alchlor that removes in the leach liquor, and then sink the processing of zinc and lead, and the sour calcium of hydration silicon (aluminium) that is generated can be used to do lightweight refractory.

Advantage of the present invention is: method and apparatus is simple, directly receives the Chemicals that purity is higher; Starting material and energy consumption are low, the economic benefit height; Pollution-free, can eliminate public hazards, obvious social benefit.

The embodiment of the invention 1, to the leach liquor (Pb=24.56g/l that contains Pb, Zn, Zn=20.69g/l) add by stoichiometry in and generate lead sulfide and required sodium sulphite solid or solution or the hydrogen sulfide of zinc sulphide, stirred under the room temperature 5～60 minutes, left standstill 1～2 hour, Zn and Pb generate precipitation (being precipitated as the mixture of zinc sulphide and lead sulfide) in the leach liquor, the leach liquor of chocolate also becomes light yellow transparent liquid gradually, analyze the Zn=1.56g/l in the leach liquor, Pb=0.89g/l, Zn in the leach liquor and Pb are precipitated as more than 95% as can be known.

The embodiment of the invention 2 contains in Zn and the Pb leach liquor to the uncured precipitation process that (contain Si=2.48g/l, Al=0.67g/t) add milk of lime or add solid lime, wherein the quality of CaO is SiO in the leach liquor ₂, Al ₂O ₃2 times of total mass, stirred 10 minutes down at 30 ℃, staticly settle three hours again to remove silicon-dioxide and the aluminium sesquioxide in the leach liquor, precipitation is through x-ray diffraction, principal phase is a calcium silicate hydrate, the content of Si and Al can be reduced to below the 0.05mg/ml in the leach liquor, and lead and zinc content are all＜1% in the throw out.

The embodiment of the invention 3 is washed zinc sulphide and lead sulfide mixture that precipitation obtains one time, puts into dilute hydrochloric acid solution, keep its pH＜5, be stirred to PH under the room temperature and no longer change, generate liquor zinci chloridi, filtering separation lead sulfide, its purity＞95% is analyzed in the oven dry of washing back.PH with liquor zinci chloridi transfers to 5～6 again, generates the zinc oxide precipitation, filters and obtains solid oxidation zinc, wash one time after the oven dry analysis, zinc oxide purity＞95%.

Claims

1, plumbous by reclaiming in iron content, manganese, zinc, the plumbous flue dust, the method for zinc adopts alkaline solution to leach flue dust, and wherein zinc and lead etc. are leached in the alkaline solution, behind separating liquid and the solid, reclaims zinc and lead from leach liquor.It is characterized in that in the leach liquor that contains zinc＜200mg/ml and lead＜200mg/ml, what add generates lead sulfide and required sodium sulphite solid or solution or the hydrogen sulfide of zinc sulphide by stoichiometry, after stirring 5～60 minutes under the room temperature, in static 2 hours, generate and be settled out the mixture of zinc sulphide and lead sulfide, put into dilute hydrochloric acid solution through washing, keep pH＜5, be stirred to pH under the room temperature and no longer change, generate liquor zinci chloridi, filtering separation lead sulfide, pH with liquor zinci chloridi transfers to 5～6 again, generation zinc oxide precipitation is filtered and is obtained solid oxidation zinc, and the purity of lead sulfide and zinc oxide all＞95%.

2, recovery method according to claim 1, the content that it is characterized in that silicon and aluminium in the leach liquor is during greater than 0.05mg/l, in leach liquor, be blended into earlier milk of lime or solid lime, the quality that makes calcium oxide in the leach liquor is silicon-dioxide and aluminium sesquioxide quality sum 1～3 times, remove silicon-dioxide and aluminium sesquioxide in the leach liquor in 3 hours, carry out sulfidizing again.

3, recovery method according to claim 1 is characterized in that adding in the leach liquor that contains zinc 20.69g/l, plumbous 24.56g/l by stoichiometry and calculates all generation zinc sulphide and the required solid Na of lead sulfide ₂S stirred 30 minutes under the room temperature, left standstill 1 hour, was settled out zinc sulphide and lead sulfide, and the residue zinc concentration is that 1.56g/l residual lead concentration is 0.89g/l in the leach liquor.

4, according to claim 1,2 described recovery methods, it is characterized in that leach liquor contains silicon concentration 2.48g/l, when containing aluminum concentration and being 0.67g/l, adding milk of lime in leach liquor, to make its calcium oxide quality be silicon-dioxide in the leach liquor and two times of aluminium sesquioxide sum, under 30 ℃, stir and staticly settled again 3 hours in 10 minutes, silicon in the leach liquor and aluminium are all reduced to below the 0.5g/l, and throw out contains zinc and all plumbous＜1%.