CN85101694A - Directly lead smelting is produced a kind of method of metallic lead - Google Patents
Directly lead smelting is produced a kind of method of metallic lead Download PDFInfo
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- CN85101694A CN85101694A CN85101694.4A CN85101694A CN85101694A CN 85101694 A CN85101694 A CN 85101694A CN 85101694 A CN85101694 A CN 85101694A CN 85101694 A CN85101694 A CN 85101694A
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Abstract
The present invention is about in oxidizing semlting technology with then under the reduction-oxidation smelted product condition, the method for being produced metallic lead by raw material containing lead.Reduction reaction is undertaken by occurring the solid carbon-contg reductive agent in the molten bath.And guarantee that the solid carbonate raw material is arranged in the molten bath, preferably Wingdale, rhombspar or soda ash also have reductive agent simultaneously.This method can apply to handle sulfide type, the leady raw materials of oxide type or sulfate type.In addition, this method applies to handle the lead carbonate raw material especially, to small part carbonate raw material be leady raw materials.
Description
The present invention is about raw material melted under oxidizing condition, and under the situation of reduction-oxidation molten product, is produced a kind of method of metallic lead by raw material containing lead.The present invention relates to handle all and can produce plumbous all kinds raw material containing lead in this way.This raw material contains lead sulfide, lead sulfate and plumbous oxide raw material and their mixture.Perhaps, raw material containing lead has smart dressing intermediates and waste material.
Recent years, in many kinds of lead smelting process programs that propose,, all include oxidizing semlting stage and and then oxidation molten bath product reduction with regard to principle.Therefore, those so-called direct plumbous melting process and those can cause into the process of plumbous molten bath of a kind of low sulfur content and high lead content slag, and can say so belongs to above-mentioned melting process class.Otto Gu Mupu technology (as German Patent 1179004), can bright gram technology (U. S. application 3847595) this special splicer's Joseph skill (metal magazine 20(12) 26-30,1969), Wal carat technology (U. S. application 3326671), all these belongs to this class Ke Fusai secret service skill (U. S. application 3555164) and Q-S technology (U. S. application 3941587).
In Pohle pauses early stage patent specification, U. S. application 4017308 and U. S. application 4008075 were spoken of other lead smelting technology that comprises smelting reduction, these technologies are relevant to oxidation and/or sulfuration or vitriol raw material, and produce metallic lead with the top blast rotary oven as melting and reducing apparatus.Spoke of similar processing method in Pohle pauses early stage publication European application 0007890 and European application 0006832, these relate to by plumbiferous intermediates in announcing, particularly those intermediates that contain high-copper and/or arsenic amount are produced metallic lead.The pause common feature of technology of these early stage Pohles is that lead is to produce in two stages of branch.In first stage, plumbous raw material and flux membership are along with the help fusing down of the band oxygen combustion flame that passes through the raw material surface in this stove, formation is with the fusion of lead pond of sulfide and oxygen enrichment lead skim form, and plumbous oxide content reaches 20-50% in the slag, generally speaking 25-50%.Second stage, coke or some other suitable reductive agents can be added in the fusion of lead pond, and when molten bath heating and stove rotation, the fusion of lead intracisternal material is therefore reduction also.
In the Pohle a afterwards patent application of pausing: Sweden application 8302486-9(it corresponding to European application 0124497) also narrated single stage process, in this stage, reductive agent adds converter with leady raw materials.This can be regarded as a process that can allow starting material oxidizing semlting and melted material reduction finish simultaneously.In the lead smelting definition that the present invention comprised, this method is arranged.
If all lead smelting processes are based on direct lead smelting technology and comprised melted material that contains plumbous oxide and experienced a reduction phase, a common feature is all arranged, Here it is reduction rate is very slow and to finish the reduction time spent quite long, if therefore considering the economy of the reductive agent reduction phase of required consumption when obtaining unit weight lead is restricted, in other words, reductive agent such as coke effective rate of utilization are very low.
Adopt direct lead smelting technology when the leaded oxidation of sulfureted intermediate product of comprehensive treating process, plumbous product per ton consumes 150 to 200 kilograms of reductive agents.As institute's consumptions coke quantity in Pohle Dun Kaer multiplex (MUX) skill by the plumbous guestimate of adding per ton, 70 kilograms of consumption reductive agents, plumbous product consumption 150-160 kilogram reductive agent correspondingly per ton, this is one of the most desirable process program of present scope.Whether the coke quantity master who is consumed can be reduced if it were not for depending in the recovery time.On the other hand, when the heat fused material is finished reduction process, consider and keep fervid melted state institute consumed energy that the shorter recovery time will be more favourable.
The quantity of the reductive agent that is consumed when the vulcanizing material of handling is the quantity that depends on the quantity of slag and its lead content of formation or depend on sulphur in the lead that is obtaining.As above-mentioned mentioned, most of so-called directly purpose of lead smelting technology all is to want the plumbiferous raw material of melting to become a kind of fusion of lead pond of low sulfur amount, can be so that plumbous through suitable lead rifining method, manufacturing contains 35%-50% lead skim product before reduction phase begins, in these processes, general plumbous output per ton consumes 100 kilograms in coal.
At present in above-mentioned the sort of lead smelting process great discovery is arranged again, use the technology of this invention, reduction process can more effectively be carried out basically.This reduction process can make reduction rate improve, and the effective rate of utilization of carbon improves.In this respect, the plumbous process economy that comprises fusing-reduction phase can greatly improve.This inventive method feature reflects in the operation stage of proposition rights protection for this purpose.
Adopting the present invention when the melt substance of gained from the oxidizing semlting process is plumbous with the reducing metal, reduction efficiency greatly improves.Use a kind of reductive agent of solid carbon-contg when reduced state, the molten state of solid carbonate raw material can be used as this reductive agent.
Coke or coal can be used as solid-state carbon containing reducer.
The carbonate raw material can be Wingdale, rhombspar or soda ash.In most of the cases, all be to select used material generally according to price.The roughness that the block size of carbonate raw material preferably has is to make the process of carbonate decomposition or oxide compound slow as far as possible.Up to the present, in the test of being carried out, find that also the Wingdale physical size can be lower than 2 millimeters Wingdales than actual size bigger effectiveness is arranged between the 2-5 millimeter.
It is not most important using the quantity of carbonate raw material.Yet, experiment finds that approximately the moiety amount with the coal of original supply reduction phase can be particularly suitable, certainly find also that lesser amt also is effective in certain limit, when for example lead tolerance is low in the less or slag when the quantity of slag, therefore can not make on the quantity of using carbonate a lower boundary in advance.The upper limit that adds carbonate only needs to consider economy.The metallurgist just can and consider to reduce reductive agent consumption under every kind of practical situation like this, reduces the carbonate add-on that recovery time and reductive agent and carbonate material price find a best.From pure technological standpoint, the carbonate add-on does not have the upper limit, unless that these problems relate to carbonate is influential to the quantity of slag and its component that generate.Yet, under most of situation, basic raw material through-stone lime stone, Manganse Dioxide or soda ash are as slag former or fusing assistant and be added to and go in the fusion process, therefore, in most of the cases, slag former and fusing assistant, it is needed and alternative or additional primary demand to this slag former or fusing assistant that the dioxide product that decompose to produce via the carbonate raw material is added in the slag.
Be added to carbonate raw material in the converter and perhaps contain the raw material of all or part of lead.In other words, leady raw materials can be the carbonate raw material whole or in part.That is to say and find to use method of the present invention, can easily the carbonate leady raw materials be handled that for example such raw material can be so and with carbon to reduce with this method melting.Because the carbonate material in the ore has quickened melting-reduction process.Containing the lead carbonate raw material can mix with other kind leady raw materials, adds the lead that necessary carbonate and certain proportion have been smelted out in this case in this process.
Solid state reduction agent and carbonate raw material in right amount, directly are added in the formed molten bath in the oxidizing semlting process and/or afterwards.Two kinds of additives need use certain special special technique at some particular stages of technological cycle in this respect, be added in the molten bath with cause these additives mutually not influence mode appoint whole molten bath to be distributed and to handle.In other words, additive is easy to discrete distribution in the material that has melted.Like this, finish in smelting period in a kind of suitable mode at these two operation stage solid feeds and to be added on the basis in molten state or the molten bath, and mix this melt substance with machinery or air operated method or other suitable method, like this, this solid feed is disperse and distributes in the molten bath.Can pass through spray gun, air port or nozzle spirt molten bath such as solid feed.In Kaldo converter, when converter forwards on the obliquity, solid feed can be ejected on the molten drop curtain that melted material drops, and solid feed soaks into rapidly on these molten drops and disperse is distributed in the melted material.Converter helps solid feed to keep disperse to distribute in melted material as far as possible for a long time to rotation, and the rotation of converter also improves the utilization ratio of reductive agent.
Most of metal carbonate, alkaline carbonate and alkali+metal carbonate decompose rapidly for 1100 ℃-1400 ℃ at smelting temperature basically, carry out the what is called calcining by this reaction
Yet an important exception is carbonic acid (B
aCO
3) only at 0.01 atmospheric pressure, 1100 ℃ of decomposition.Therefore, when disperse was distributed in that carbonate is heated in the molten bath, carbonate decomposition produced carbonic acid gas and overflows.The partial CO 2 that generates according to following reaction formula will generate carbon monoxide with the solid carbon reaction in the reductive agent.
Therefore the carbon monoxide that generates will help reduction reaction to carry out sooner.To a certain extent, increases the molten bath and stir, and carbon monoxide directly produces in the molten bath and because gas one solid reaction faster:
Reaction will appear consolidating simultaneously.
Contact for making in the molten bath reductive agent reach frequent, before they are put into the molten bath, just should mix with the carbonate raw material.For example mix with the reductive agent of milling.
With reference to several working examples further in detail to describe the present invention; The method according to this invention also can compare with some previous methods and process.
Example 1
A) have 48.20 tons of lead sulfide washed ores of following major ingredient:
47.0%Pb, 11.8%Fe, 7.2%Zn, 22.4%S and 3.3%SiO
2Inject in many formulas of Ka Er top blown converter by an air port with 3.8 tons of silicon-dioxide.This converter internal diameter 2.5M adds raw material and 10800Nm
3Oxygen and 12490Nm
3Air is flash smelting in stove.The whole time length of flash smelting technology is 220 minutes, and after this, 0.8 ton of coke is added in the molten bath, and the material in the molten bath also material needs 100 minutes.In this reduction process, use oil one an oxygen burner to make that temperature approximately maintains 1300 ℃ in the molten bath, this moment, oil supply was 51409.About 12 tons of fusings that contain 0.20% sulphur lead then from stove, pour out together with the slag that contains 4.70% lead.Like this, about plumbous product per ton consumes coke 6.7Kg.
B) in another melting cycle, the class leady washed ore of above-mentioned quantity is carried out flash smelting together with similar silica additive in converter.In this situation, oxygen depletion 10730Nm
3, and air consumption is 10990Nm
3Flash smelting technology continues 205 fens clock times, and after this, particle size is the 2-5 millimeter, and the Wingdale of 0.8 ton of coke and 0.3 ton is added in the converter.Having now may be short in 65 minutes the reduction reaction time, and the consumption of oil is 468 liters in this reduction reaction.Obtain 14 tons of lead that melted and contain the slag of 4.2% lead and by pouring out in the converter.Plumbous content is lower than the lead tolerance that obtains slag in the above-mentioned melting cycle in the slag like this.Plumbous product per ton consumes coke and also drops to about 50 kilograms.
These relatively tend to illustrate a kind of carbonate additive, at this situation Wingdale, require the recovery time shorter and the coke loss is lower when reduced state basically.
Example 2
30.6 tons of plumbous washed ores of identical furnace charge with example 1 are mixed together for 19.0 tons with the sulfurous gas powder leady raw materials that approximately contains 62% lead, and with 2.4 tons of sulfurous gas flash smeltings in the sort of converter described in the example 1 together.In 150 minutes flash smelting cycles, in this process, to consume 9180Nm
3Oxygen and 6960Nm
3Air.On finishing the fusion process basis and 0.5 ton of coke of the same particle size of being mentioned among the routine 1b and 0.3 ton of Wingdale be added in the converter.The molten bath is through after 50 minutes reduction reactions, and lead content has dropped to 3.1% in the slag.During reduction reaction,, spend 336 liters of oil in order to keep bath temperature.Sulfur content be 0.33%19 ton fusing lead and lead tolerance be that 3.1% slag is poured out by converter together.In this case, plumbous product per ton consumes approximately only 25 kilograms in coke between reduction period.
Example 3
61.6 the plumbous washed ore of ton sulfur-bearing, carbonate is by following major ingredient:
53.1 plumbous, 6.7% zinc, 19.4% sulphur (wherein 12% sulfide sulfur), 7.9% iron, 3.0% silicon-dioxide+alchlor and 1.36% carbon (occurring) and 2500Nm with carbonate form
3Oxygen carries out flash smelting.Smelt stage continues 165 minutes.40 tons of silicon-dioxide and 11 tons of Wingdales are added in the converter with the flux form.Finish on the basis at fusion process, 1.1 tons of coke are added in the converter, because reduction reaction is being carried out in the molten bath, keep bath temperature with a kind of oil-carrier of oxygen burner heating.The reduction reaction stage continues 120 minutes.Consumed 634 liters oil in this stage.1.0%27 tons of slags of lead tolerance and lead tolerance are that 99.5%18.5 ton lead is by pouring out in the converter.Produce plumbous about 60 kilograms of the coke quantity survey that consumes per ton.
Example 4
36.3 the plumbous washed ore major ingredient of the main carbonate containing lead ore of ton is: 58.1% lead, 8.3% zinc, 3.5% sulphur, (wherein 2.0% sulfide sulfur), 1.2% iron, 2.0% silicon-dioxide+alchlor and 4.3% carbon (existing with carbonate form) are in six batches, general 20 minutes intervals and 4.3 tons of flux, the lead ore of 7 tons of vitriol sludges and 3.3 tons of granular iron olive rock ballasts, and and 0.8 ton of coke add together in the converter of many formulas of Ka Er, as being introduced in the example in front.Furnace charge helps melting through preheating and with an oily carrier of oxygen burner, and heating and melting furnace charge time are 30 minutes.The consumption of oil is 2800 liters.
Claims (8)
1, produces the method for metallic lead by leady raw materials, adopt under oxidizing condition melting raw material and reduction-oxidation melting material property to be that having melted material and assurance with the solid-state carbon containing reducer reduction that is in melted state contains carbonate solid feed and reduction and reductive agent and be in the melted state simultaneously.
2,, be characterised in that reductive agent is coal and coke according to claim 1 method.
3,, be characterised in that at least a portion carbonate raw material has Wingdale, rhombspar and/or soda ash according to claim 1-2 method.
4,, be characterised in that the plumbiferous raw material of at least a portion has the carbonate raw material according to claim 1-2 method.
5, according to one of any method of claim 1-4, be characterised in that reductive agent and carbonate containing raw material, among being in the oxidizing semlting process and/or after directly be added in the molten bath.
6,, be characterised in that reductive agent and carbonate containing raw material are by in spray gun, air port or the direct spirt of the nozzle molten bath according to claim 5 methods.
7,, be characterised in that carbonate raw material and reductive agent mix outside the melting molten bath according to one of any method of claim 1-6.
8,, be characterised in that above-mentioned carbonate raw material and reductive agent mix with method for grinding or mix with pulverizing above-mentioned reductive agent according to claim 7 methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101694 CN1003654B (en) | 1984-02-07 | 1985-04-01 | Method for producing metallic lead by direct lead-smelting |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8400624A SE441189B (en) | 1984-02-07 | 1984-02-07 | PROCEDURE FOR MANUFACTURING METALLIC LEAD THROUGH MELT REDUCTION |
| CN 85101694 CN1003654B (en) | 1984-02-07 | 1985-04-01 | Method for producing metallic lead by direct lead-smelting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101694A true CN85101694A (en) | 1987-01-31 |
| CN1003654B CN1003654B (en) | 1989-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101694 Expired CN1003654B (en) | 1984-02-07 | 1985-04-01 | Method for producing metallic lead by direct lead-smelting |
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| CN (1) | CN1003654B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461849A (en) * | 2017-02-20 | 2018-08-28 | 中国瑞林工程技术有限公司 | The processing system of lead-acid battery and its application |
| CN113684372A (en) * | 2021-07-29 | 2021-11-23 | 昆明贵研新材料科技有限公司 | Method for recovering platinum group metal from spent automobile catalyst |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039027C (en) * | 1995-06-22 | 1998-07-08 | 中国石油化工总公司 | Extreme-pressure anti-wear composite additive |
| CN1317232C (en) * | 2006-01-18 | 2007-05-23 | 北京工业大学 | Lightweight foamed ceramic tile preparation method |
| CN101864522B (en) * | 2010-06-28 | 2012-07-25 | 中南大学 | Clean metallurgical method for low-temperature molten salt of lead |
-
1985
- 1985-04-01 CN CN 85101694 patent/CN1003654B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108461849A (en) * | 2017-02-20 | 2018-08-28 | 中国瑞林工程技术有限公司 | The processing system of lead-acid battery and its application |
| CN113684372A (en) * | 2021-07-29 | 2021-11-23 | 昆明贵研新材料科技有限公司 | Method for recovering platinum group metal from spent automobile catalyst |
| CN113684372B (en) * | 2021-07-29 | 2022-09-16 | 昆明贵研新材料科技有限公司 | Method for recovering platinum group metal from spent automobile catalyst |
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| Publication number | Publication date |
|---|---|
| CN1003654B (en) | 1989-03-22 |
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