CN103482580B - Method for recycling elemental sulphur from ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy high-sulphur residues - Google Patents
Method for recycling elemental sulphur from ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy high-sulphur residues Download PDFInfo
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- CN103482580B CN103482580B CN201310422340.9A CN201310422340A CN103482580B CN 103482580 B CN103482580 B CN 103482580B CN 201310422340 A CN201310422340 A CN 201310422340A CN 103482580 B CN103482580 B CN 103482580B
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Abstract
The invention relates to a method for recycling elemental sulphur from high-sulphur residues produced in an ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy process. According to the technical scheme, rapid temperature and pressure rising is conducted on oxygen immersion during ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy, flash evaporation is conducted, and then the melted elemental sulphur is cooled into granular solid elemental sulphur after the elemental sulphur is separated in a hot filtration mode. The method has the advantages that by means of rapid temperature and pressure rising, a small reactor is added to an existing ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy system, equipment is simple, investment is low, the existing production system is not affected, process procedures are short, operation is easy, and the zinc concentrate ordinary-pressure oxygen-enrichment direct hydrometallurgy process is perfected.
Description
Technical field
The present invention relates to a kind of method reclaiming elementary sulfur from the high sulphur slag of the direct Zinc Hydrometallurgy Process output of normal pressure oxygen enrichment.
Background technology
In conventional zinc hydrometallurgy, fluidized bed roasting is adopted to zinc concentrate, sulphur oxidized formation SO
2enter flue gas and produce sulfuric acid.And in the direct zinc hydrometallurgy of normal pressure oxygen enrichment, normal pressure oxygen enrichment is adopted directly to leach (95 DEG C to zinc concentrate, atmospheric pressure, pass into the oxygen that more than 98% oxygen is dense), sulphur oxidized forming element sulphur produces a large amount of high sulphur slag, both at home and abroad all less than the industrial practice reclaiming elementary sulfur in the high sulphur slag from the direct Zinc Hydrometallurgy Process output of normal pressure oxygen enrichment.This high sulphur slag is mostly placed on special slag field as waste abroad and stores up, and this high sulphur slag is because being rich in the valuable metals such as silver at home, need by after recovery of elemental sulfur, and the valuable metals such as silver obtain enrichment and reclaim further.This high sulphur slag is that after can not adopting Steam Heating melting, the method for heat filtering produces elementary sulfur, directly can not drop into lead system in a large number because sulfur-bearing is too high simultaneously and cause sulphur uneven, this high sulphur slag can only adopt interim slag field to store up, and causes huge environmental protection pressure.The valuable metals such as the silver that high sulphur slag is overstocked simultaneously can not reclaim, and cause deficiency in economic performance.
Traditional fluidized bed roasting can be adopted to carry out desulfurization to this normal pressure oxygen enrichment direct zinc hydrometallurgy high sulphur slag, sulfur-containing smoke gas send relieving haperacidity to produce sulfuric acid, slag send the valuable metals such as lead system recover silver, integral production technological process is complete, but do not reach the object reclaiming elementary sulfur from high sulphur slag, just the roasting relieving haperacidity of zinc concentrate is changed into the roasting relieving haperacidity of high sulphur slag, a kind of simple short processes flow process is reduced into again a kind of traditional farm labourer's process flow of complexity.Owing to can not reclaim elementary sulfur in the high sulphur slag from the direct Zinc Hydrometallurgy Process output of normal pressure oxygen enrichment, thus this zinc concentrate normal pressure oxygen enrichment direct leaching process is incomplete.
Summary of the invention
The object of this invention is to provide one and reclaim elementary sulfur from the direct zinc hydrometallurgy high sulphur slag of normal pressure oxygen enrichment, greatly reduce the sulphur of high sulphur slag, and wait valuable metal grade to be beneficial to further recovery for improving further silver, perfect zinc concentrate normal pressure oxygen enrichment direct leaching process.
Technical scheme of the present invention is:
1) by the oxygen immersion liquid in direct for normal pressure oxygen enrichment zinc hydrometallurgy, in reactor, pass into oxygen and steam to be rapidly heated boosting; Wherein temperature is 110 ~ 150 DEG C, pressure 450 ~ 1100Kpa, and partial pressure of oxygen is 250 ~ 800Kpa;
2) the HTHP oxygen immersion liquid obtained in step 1) is carried out flash distillation by flash tank;
3) flotation is carried out in the oxygen immersion liquid after flash distillation and obtain high sulphur slag;
4) high sulphur slag heating is obtained the elementary sulfur of molten condition;
5) step 4) is obtained high sulphur slag and carry out heat filtering output melting elementary sulfur.
6) adopt granulator, adopt water cooling to become granular solids elementary sulfur to melting elementary sulfur.
The applicant is found by research: the high sulphur slag sulfur-bearing that the direct Zinc Hydrometallurgy Process of normal pressure oxygen enrichment produces reaches 70 ~ 80%, and at the temperature of about 150 DEG C, the sulphur in these high sulphur slags can not be separated in melting; Be greater than at the temperature of 400 DEG C, elementary sulfur distillation in high sulphur slag can be being become gaseous state, under the condition of isolated air, can elementary sulfur be obtained through condensation.But adopt this way of distillation to reclaim elementary sulfur from high sulphur slag and bring two vital problems, one is that equipment is complicated, and quantity is many, and investment is large, especially requires to distill in isolated air conditions, is applied to large-scale industrial production unrealistic; Two is that way of distillation operating cost is high, and the sulfur recovery for low value adopts the way of distillation to lose more than gain.
Applicant is found by research: 10 ~ 20% be sulfate form in element sulphur in the high sulphur slag that the direct Zinc Hydrometallurgy Process of normal pressure oxygen enrichment produces, 90 ~ 80% is elementary sulfur form.In high sulphur slag, elementary sulfur crystal formation is different just, makes at 150 DEG C of temperature, and in these high sulphur slags, elementary sulfur can not melting, and after also just cannot adopting simple Steam Heating, the mode of heat filtering reclaims elementary sulfur from high sulphur slag.
Therefore, the applicant proposes first to carry out high-temperature process to the normobaric oxygen immersion liquid in the direct zinc hydrometallurgy of normal pressure oxygen enrichment, and the oxygen immersion liquid under HTHP is carried out flash distillation by flash tank, the crystalline structure of element sulphur is wherein changed, then the oxygen immersion liquid after flash distillation is obtained high sulphur slag by FLOTATION SEPARATION, again the high sulphur slag after this process is heated, melting sulphur wherein, and be separated.
Because the pressure general control when carrying out high temperature high pressure process to oxygen immersion liquid is at 450 ~ 1100Kpa, therefore, pressure in flash tank will be starkly lower than 450Kpa, such as 200Kpa, be the oxygen immersion liquid of high-temperature pressure by the oxygen immersion liquid step-down of HTHP by flash distillation, to meet the requirement of subsequent handling process.
Heat treatment is carried out to the high sulphur slag obtained according to the inventive method, to obtain molten sulfur, when being convenient to be separated further, preferably adopts steam-heated method.Those skilled in the art can also adopt additive method to heat high sulphur slag.
The equipment of fractional melting sulphur can select blade filter press to carry out heat filtering output melting elementary sulfur.Filter residue simultaneously after separate sulfur is rich in the valuable metals such as silver, to reclaim further.
Water cooling is adopted to become granular solids elementary sulfur melting elementary sulfur by granulator.
The invention has the advantages that:
1) utilize the method for the boosting that is rapidly heated, in the direct wet zinc-making system of existing normal pressure oxygen enrichment, increase the reactor of small size, equipment is simple, and small investment, does not affect existing production system.
2) utilize flash process, elementary sulfur crystalline structure in high sulphur slag is transformed, can melting at 150 DEG C of temperature.
3) owing to changing elementary sulfur crystalline structure in high sulphur slag, after adopting Steam Heating, the method for heat filtering reclaims elementary sulfur, and belong to physical process, technological process is short, and equipment is simple, and processing ease, production cost is low.
4) from normal pressure oxygen enrichment direct zinc hydrometallurgy high sulphur slag sulphur to elemental sulfur product direct yield > 85%, S > 99.5%.
5) perfect zinc concentrate normal pressure oxygen enrichment direct leaching process.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Detailed description of the invention
Embodiment 1
The technique of the direct zinc hydrometallurgy of normal pressure oxygen enrichment is: zinc concentrate enters reactor through ore grinding, adds waste electrolyte, passes into the dense oxygen of more than 98% oxygen and steam, carry out normal pressure oxygen enrichment directly to leach, control temperature 95 DEG C, atmospheric pressure, reaction time > 24h.
Briefly introduce technique and the parameter of the direct zinc hydrometallurgy of normal pressure oxygen enrichment
1) by the high-temperature pressure oxygen immersion liquid (95 DEG C in the direct zinc hydrometallurgy of normal pressure oxygen enrichment of above-mentioned acquisition, atmospheric pressure) be placed in reactor, pass into oxygen and steam, carry out the boosting that is rapidly heated, reaction time 20 ~ 40min, temperature 110 ~ 150 DEG C, pressure 450 ~ 1100Kpa, wherein oxygen partial pressure is 250 ~ 800Kpa.
2) the HTHP oxygen immersion liquid after the above-mentioned boosting that is rapidly heated is placed in flash tank and carries out flash distillation, temperature 102 ~ 120 DEG C in flash tank, pressure 200Kpa.
3) flotation is carried out to the oxygen immersion liquid after flash distillation, flotation divide roughly select, selected, scan three sections of operations, control flotation temperature 60 ~ 80 DEG C, the blowing pressure 100 ~ 300Kpa.Obtain high sulphur slag, output low-sulfur slag send Slag treatment simultaneously.
4) above-mentioned high sulphur slag is added in sulfur melting pool, pass into Steam Heating and carry out melting, control temperature 150 DEG C.
5) adopt blade filter press, carry out heat filtering, filter pressure 500 ~ 800Kpa, temperature 150 DEG C, output melting elementary sulfur to melting high sulphur slag, the hot filter residue of output is rich in silver and waits valuable metal to reclaim further simultaneously.
6) adopt granulator, adopt water cooling to become granular solids elementary sulfur to melting elementary sulfur.
Claims (3)
1. from the direct zinc hydrometallurgy high sulphur slag of normal pressure oxygen enrichment, reclaim the method for elementary sulfur, it is characterized in that comprising the steps:
1) by the oxygen immersion liquid in direct for normal pressure oxygen enrichment zinc hydrometallurgy, in reactor, pass into oxygen and steam to be rapidly heated boosting;
Wherein temperature is 110 ~ 150 DEG C, pressure 450 ~ 1100kPa, and partial pressure of oxygen is 250 ~ 800kPa;
2) the HTHP oxygen immersion liquid obtained in step 1) is carried out flash distillation by flash tank;
3) flotation is carried out in the oxygen immersion liquid after flash distillation and obtain high sulphur slag;
4) high sulphur slag is passed in sulfur melting pool steam and carry out melting;
5) melting high sulphur slag is carried out heat filtering output melting elementary sulfur by blade filter press;
6) adopt granulator, adopt water cooling to become granular solids elementary sulfur to melting elementary sulfur.
2. according to the method reclaiming elementary sulfur from the direct zinc hydrometallurgy high sulphur slag of normal pressure oxygen enrichment described in claim 1, its
Be characterised in that step 2) in flash temperature be 102 ~ 120 DEG C, pressure 200kPa.
3. according to the method reclaiming elementary sulfur from the direct zinc hydrometallurgy high sulphur slag of normal pressure oxygen enrichment described in claim 1, its
Be characterised in that step 4) in the method for melting high sulphur slag be pass into steam, and control temperature is 145 ~ 155 DEG C.
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| CN201310422340.9A CN103482580B (en) | 2013-09-17 | 2013-09-17 | Method for recycling elemental sulphur from ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy high-sulphur residues |
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| CN201310422340.9A CN103482580B (en) | 2013-09-17 | 2013-09-17 | Method for recycling elemental sulphur from ordinary-pressure oxygen-enrichment direct zinc hydrometallurgy high-sulphur residues |
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| CN103482580B true CN103482580B (en) | 2015-04-29 |
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| CN104445084A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Method for recovering sulfur from zinc-leached sulfur-containing residues |
| CN104445083A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method for sulfur ore concentrate |
| CN109593959A (en) * | 2018-12-24 | 2019-04-09 | 重庆工程职业技术学院 | A kind of pyrolusite and zincblende joint oxygen press acid leaching process |
| CN111392696A (en) * | 2020-04-26 | 2020-07-10 | 中国恩菲工程技术有限公司 | Device and method for recovering elemental sulfur in sulfur-containing hydrometallurgy slag |
| CN111874870B (en) * | 2020-08-11 | 2023-08-18 | 中南大学 | Device and method for regulating and controlling element sulfur crystallization transformation in zinc smelting high-sulfur slag |
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| CN101734626A (en) * | 2009-11-23 | 2010-06-16 | 长沙有色冶金设计研究院 | Method for recovering sulfur element from zinc sulphide concentrate direct leaching residues |
| CN102796868A (en) * | 2012-09-12 | 2012-11-28 | 长沙有色冶金设计研究院有限公司 | Production process for directly leaching zinc from zinc sulfide concentrate |
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