CN104060091A - Low-grade valuable metal leaching-biosorption-electrodeposition hydrometallurgy process - Google Patents
Low-grade valuable metal leaching-biosorption-electrodeposition hydrometallurgy process Download PDFInfo
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Abstract
The invention provides a low-grade valuable metal leaching-biosorption-electrodeposition hydrometallurgy process, belonging to the technical field of hydrometallurgy process. The low-grade valuable metal leaching-biosorption-electrodeposition hydrometallurgy process comprises the following steps: adding a biomass adsorbant in low-grade valuable metal mineral powder pickle liquor or valuable metal-containing acidic wastewater, stirring for reaction, then filtering the biomass adsorbant to obtain biomass adsorbant powder with enriched trivalent metal iron ions and filtrate rich in other valuable metals; repeatedly washing the biomass adsorbant powder with clean water, drying, placing in a tube furnace, performing a thermal decomposition reaction to obtain ultrafine metal iron powder; and recovering the valuable metals from the filtrate in an extraction-electrodeposition or biosorption-electrodeposition manner. The prepared ultrafine metal iron powder and hydrogen peroxide can be used for treating wastewater under the condition of a certain pH. The low-grade valuable metal leaching-biosorption-electrodeposition hydrometallurgy process has the remarkable advantages of environment friendliness, cleanness, high efficiency, and full utilization of resources, and has a popularization and application value and a prospect of improving the existing hydrometallurgy process.
Description
Technical field
The present invention relates to hydrometallurgical processes technical field, refer to especially a kind of for low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes.
Background technology
In recent years, non-ferrous metal rich ore is through exploitation for many years, abundant ore source is more and more rare, and part is even exhausted, therefore from various low-grade mine tailings, assorted ore deposit and metallurgical slag, extracts the important directions that valuable metal has become Non-ferrous Metallurgy development.
Hydrometallurgy is the choice of technology that is applicable to very much processing this class low-grade mineral resource, Bioleaching-Extraction electrodeposition the technology growing up such as smelting for Treating Low-grade Copper Ores, become at present the blanket wet method in worldwide Nei Ge great copper mine smeltery and carried copper technology, similarly, the Leaching-solvent Extraction-electrowinning Technology of low-grade zinc has also obtained many research and probes in recent years.From the validity of technology and the economy of extraction cost, comprehensively analyze, can judge, leaching-Extraction electrodeposition technology will be the technological development direction becoming more and more popular in all kinds of low-grade nonferrous metals ore industrial abstracts field.Succeeding in developing of LIX series special efficacy copper extractant, has caused the success of the industrialization broad practice of Treating Low-grade Copper Ores wet type copper smelting technique in the past few decades.And aspect the leaching of low grade ore or slag, go through development for many years, and having there is the comparatively economically viable extensive leaching-out techniques such as dump leaching, Bioleaching, the technical development of this respect is comparative maturity relatively.The extraction of the low grade ore of all kinds of valuable metals, slag and even its secondary resource more and more relies on the development of hydrometallurgical technology, and will be directly connected to as the optimization of " leaching-Extraction electrodeposition " process of critical process flow process every technico-economical comparison that wet method is extracted, the various innovative approachs that therefore launch round this gordian technique flow process also emerge in an endless stream.
The present invention is directed to the multiple puzzlement that this main process usually runs in engineering site practice and disclose a kind of improved novel method, biosorption technology is incorporated in above-mentioned traditional " leaching-Extraction electrodeposition (L-SX-EW) " technique, form follow-on hydrometallurgical extraction novel process, the invention discloses two kinds of designs of the hydrometallurgy new process for low-grade nonferrous metals ore, be " leaching-biological adsorption-Extraction electrodeposition " novel process, another kind is " leaching-biological adsorption-electrodeposition " novel process.
Two puzzlements that these two kinds of hydrometallurgy new process run into often mainly for concentration of valuable metals ion from infusion solution: one, the problem that iron disturbs.In hydrometallurgy process, iron is one of modal impurity element in all kinds of nonferrous metals ores, it appears in infusion solution, it is almost very general thing, the place of perplexing is most: iron ion almost all can have precedence over valuable metal ions as copper in all wet method extraction means, zinc, nickel, cobalt, bismuth, indium etc. and extracting, if adopt the precipitator method, extract the valuable metal ions in immersion liquid, iron ion can preferentially precipitate so, the typical precipitator method have jarosite process, goethite process, hematite process lamp, but these precipitator method operations are complicated, need to consume a large amount of chemical reagent, producing the large and ferro element of the quantity of slag is difficult to be utilized effectively and puts aside as useless, directly neutralization precipitation only can cause colloid ironic hydroxide and cause sweeping along of more valuable metal ions, co-adsorption and co-precipitation is lost, therefore, precipitator method deironing also be unable to do without the interference problem of iron.For solving the above shortcoming of crystalline deposit method deironing, people have carried out various explorations and research, expect to develop better method for removing iron.Extraction process deironing is that research is more a kind of, based on ferric ion easily by the take the lead in feature of extracting and enriching of most extraction agents, as P204, P507, Cyanex272,3,5-di-isopropyl Whitfield's ointment, tertiary amine etc., but the Fe being extracted (III) ion is difficult to back extraction, furthermore Fe (III) ion pair organic extractant have certain oxidative degradation with and be easily hydrolyzed and cause extraction process generation emulsion, add the low value of the expensive and iron of extraction agent, cause extraction process deironing seldom to be promoted the use of at large in the industrial of reality.So extraction agent deferrization method also could not solve the existing problems of traditional crystallization precipitator method deironing.Obviously, iron interference problem become a ubiquity in hydrometallurgy field, with the challenge of intercommunity.Two, the problem that extraction efficiency is low.Such as, for Low Grade Copper Ore resource, leaching-Extraction electrodeposition be the most effectively, the most blanket metallurgical technology.Although the method is widely used industrial, but its some outstanding shortcomings still need to overcome, such as extraction agent is expensive, while easily there is emulsification, low temperature region or microthermal climate, extraction system viscosity is large, and on the low side and affect extracting and enriching effect etc. for copper ion concentration in the leaching solution of Treating Low-grade Copper Ores, be all the problem generally easily running in extraction process.Therefore, above two problems have brought new opportunities and challenges also to the development of traditional " leaching-Extraction electrodeposition " technique, if can manage, iron is disturbed and low these two problems of extraction agent efficiency in addition improvement to a certain degree even solve, be expected to make more promoter action for hydrometallurgy industrial expansion.
Wherein, one of major objective that the first " leaching-biological adsorption-Extraction electrodeposition " novel process proposes designs for " iron interference ", wherein the effect of biological adsorption is exactly deferrization, its ultimate principle is to utilize biological adsorption agent generally the preferential adsorption phenomena of ferric ion to be realized to removing iron contamination in the leaching solution of all kinds of valuable metals, to be that follow-up extraction process is got rid of the interference of iron, thereby improve the efficiency of existing extraction process; Another major objective that this technique proposes be use biological adsorption deironing after, continuing to add biological adsorption carries out enrichment in advance and concentrates the valuable metal ions in lower concentration leaching solution, resupply next process extracting and enriching, after this biological adsorption preconcentration once, the valuable metal ions solution of higher concentration is conducive to raising and the improvement of extraction efficiency, can be also therefore a useful promotion to existing extraction process.
" leaching-biological adsorption-electrodeposition " novel process of the second design, for the enrichment of valuable metal ions in the leaching solution of some lower concentrations, to extract specially, while adopting abstraction technique to extract, efficiency is very low, approached extraction in limited time lower, the economical and efficient that the technology that can consider to use instead biological adsorption realizes lower concentration valuable metal ions extracts.In concrete practice, can consider first to adopt biological adsorption by the adsorbing and removing in advance of the iron ion in leaching solution, and then add biological adsorption agent the valuable metal ions Extraction and enrichment in leaching solution is got up, and obtain concentrated valuable metal ions solution through desorb, then reclaimed through electrodeposition technology.
This technique is successful energy powder body material by the biological adsorption agent material that has adsorbed iron, starting material for fields such as environmental purification, soil remediation, thereby realized the reasonably combined use of resource in different subjects, different field, thereby realized full-range thoroughly clean, friendly and green process.
In aforesaid hydrometallurgy new process, adopt biomass absorbent method to carry out optionally deferrization, make iron realize recovery in the mode of higher degree; And the iron that absorption is obtained or concentrated use as reagent iron through desorb, or directly through original position thermal reduction, make iron powder without desorb, for purifying water process.In the present invention, special recommendation offers purifying water process industry by made ultra-fine zeroth order iron powder, such as adsorption cleaning material, can also react source of iron used as Fenton oxidation, thereby for the various application places of Fenton's reaction, as the degraded of organic waste water is disinfected etc. all many-sides without poisoning processing, oxidation disinfection.
The biological adsorption agent wide material sources that adopt due to know-how disclosed by the invention, cheaply, cost of manufacture is cheap, to the advantages of good adsorption effect of iron ion, (selectivity is strong, loading capacity is high, rate of adsorption is fast) etc. overall merit, make the leaching solution of pending various valuable metals, the iron that can realize is wherein quick, be adsorbed and remove easily, and other valuable metal ions that coexist also can be effectively suppressed by amount co-adsorption and loss, so the iron purity obtaining is higher, be expected to have good recycle value, furthermore absorbent particles is larger, settleability is good, easily realize solid-liquid separation.So, the flood tide that existing hydrometallurgy industry produces is rich in the leaching solution of iron, can the change one's identity suddenly source of iron of horn of plenty, supply with the needed a large amount of superfine iron powder of purifying water process industry as sorbent material, and widely used Fenton reagent ferrous source material used, thereby greatly reduce the cost of sorbent material water-purifying material and the reagent cost of Fenton's reaction, for these iron resourcess that are considered as waste by traditional deferrization method have found a wide Application Areas, and provide a kind of and can accept economically, technical feasible simple and direct technology.The iron powder that adopts this method to prepare, fine size is small and scattered, reactive behavior is high, low price, wide material sources and enriching, the ferrous ion chemical reagent that comparable traditional iron powder adsorption agent preparation and Fenton's reaction adopt is more economized, and applies the convenient Separation and Recovery of method that excessive source of iron can adopt solid-liquid separation, is unlikely to remain in the aqueous solution after processing and causes reagent surplus and removing pollutant water.If biological adsorption agent adopts those agriculturals, the upper waste producing is done raw material, for these agricultural wastes biomass resources, found again the mode of a good higher value application, thereby realize recycling economy growth pattern and the novel approach that utilizes of agriculture field, being expected provides new practical technological approaches and wide Application Areas, just a good technological approaches that benefited a, arrow three is carved in many ways for the development of novel agricultural.
Therefore, due to biological adsorption agent material source extensively, be cheaply easy to get, and preparation process is simple, convenient, green clean, this feature based on biological adsorption agent, and combine with " metal-Extraction electrodeposition " technical process of existing hydrometallurgy, by bio-waste raw material, do cheap, efficient, the environment amenable advantage that sorbent material has, construct novel efficient wet New Metallurgical Technology process.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes.
This processing step is as follows:
First, get iron content and valuable metal Zn, Cu, Ni, Co, In, the grade of Bi is lower than 1% valuable metal breeze pickling liquor or containing Fe and valuable metal Zn, Cu, Ni, Co, In, the acid waste water of Bi, by adding metal mining powder of the same race, regulating the pH value of pickling liquor or acid waste water is 2～3, add biomass absorbent agent material, the addition of biomass absorbent agent material is that every liter of pickling liquor or waste water add 0.1～300g, stirring reaction 100～300min, filter, obtain being enriched with the biomass adsorbent powder of trivalent metal iron ion and the filtrate of being rich in other valuable metals,
Wherein, biomass absorbent agent material, according to disclosed method preparation in patent No. ZL:201210019530.1, is about to contain-COOH ,-SH ,-NH after washing
2,-(phenol) biomass of OH isoreactivity functional group, as being uniformly mixed according to the mass ratio of 1:0.05-0.2:0.5-2 with alkali, water, garlic slag, mangosteen slag, marine alga, vinasse, tangerine slag, Pericarpium Mali pumilae, pomelo peel etc. react, stir 12～24 hours, filter, obtain solid product, wherein, described alkali is oxide compound, oxyhydroxide, carbonate, supercarbonate or volatile salt, bicarbonate of ammonia, the urea of lithium, sodium, potassium, calcium, magnesium, one or two or more kinds mixing in ammoniacal liquor; Above solid product is washed with water until neutral, send into vacuum drying oven, temperature be 60～120 ℃ dry, ovens dry thing is smashed, is sieved, the following particle collection of 40 order obtains biomass absorbent agent material.
Then, be rich in filtrate and the extraction agent P of valuable metal
204contact, extraction valuable metal ions wherein, through washing, back extraction, obtain the solution that contains valuable metal, supply with the valuable metal that electrodeposition operation has reclaimed heavy industry, or be rich in filtrate and the biomass adsorbent contact reacts of valuable metal, absorption valuable metal ions wherein, obtains through washing, desorb the solution that contains valuable metal, supplies with electrodeposition operation and has reclaimed valuable metal wherein;
Finally; be enriched with the biomass adsorbent powder of trivalent metal iron ion after distilled water repetitive scrubbing 2～3 times; put into the baking oven hot-air seasoning 6～8h of 60～80 ℃; the dry absorbent powder of gained is laid in porcelain boat; put into tube furnace; in vacuum, pass under the condition of protective gas (hydrogen, argon gas, nitrogen, carbonic acid gas) or reactive gas (air); thermal degradation at the temperature of 400～600 ℃; make metallic iron powder; pass through again grinding, screening, classification, obtain the superfine metal iron powder of granularity below 200 orders.
Prepared superfine metal iron powder is 1 gram according to mass volume ratio: the ratio of 0.1-10 milliliter hydrogen peroxide, the pH of regulator solution is in 1～6 scope, carry out stirring reaction, preparation obtains having the Fenton's reaction system of strong oxidation capacity, for improvement and the purifying treatment of trade effluent.
The beneficial effect of technique scheme of the present invention is as follows:
In such scheme, for iron interference problem and the extraction efficiency problem on the low side running in existing Leaching-solvent Extraction-electrowinning Technology flow process provides effective technical scheme, and provide one can accept economically the higher value application that adsorbs the iron ion resource simultaneously, technical feasible novel technological approaches, be expected to realize the high-efficiency resource recycling of iron resources in hydrometallurgy trade effluent, for the reaction of the required ultra-fine zeroth order iron powder of water treatment and Fenton oxidation provides cheap, source is sufficient, active high, the Novel iron source material that rare ferron is residual, also the heavy metal ion that may contain in trade effluent together adsorbing and removing can be purified simultaneously, thereby realize the comprehensive regulation of many metal ions waste water such as all kinds of iron content in hydrometallurgy field.
Accompanying drawing explanation
Fig. 1 is schematic diagram of take leaching-absorption deironing-extracting and enriching valuable metal-electrodeposition process that copper is example of the present invention;
Fig. 2 is schematic diagram of take leaching-absorption deironing-adsorption and enrichment valuable metal-electrodeposition process that copper is example of the present invention.
Embodiment
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, be described in detail below in conjunction with the accompanying drawings and the specific embodiments.
The present invention is directed to the deficiency that existing low-grade metal minerals " leaching-Extraction electrodeposition " technique exists, a kind of low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes is provided.
Embodiment 1
Adopt the technological principle of " leach-absorption deironing-extracting and enriching valuable metal-electrodeposition " as shown in Figure 1, get 2 kilograms of certain real estate low-grade zinc powder (100 orders sieve), by solid-to-liquid ratio, be that 1:10 adds the sulfuric acid of 0.5M to carry out agitation leach, and after being heated to 90 degrees Celsius, keep agitation leach after 3 hours, filter, gained filtrate is taken out to 18 liters, and adding new zinc ore powder, to make its pH be 2.3, filters and obtain filtrate for later use;
Record iron content 4.6g/L in filtrate, zinc 6.3g/L, drops into 500 grams of garlic waste granule adsorbents, and stirring reaction is after 120 minutes, and by absorbent filtering, the concentration of iron recording in filtrate is 0.4g/L, zinc 6.2g/L, then adopt extraction agent P
204with solution contact reacts, extraction zine ion wherein, and obtain through washing, back extraction the zinc solution that concentration is 43.2g/L, further supply with galvanic deposit operation and reclaim zinc metal wherein.
Adsorbed the sorbent material of iron with after distilled water wash 3 times, the baking oven hot blast of putting into 60 ℃ dries 6 hours; The dry sorbent material of gained is put into porcelain boat tiling and open, put into tube furnace, pass into nitrogen, gas velocity is 1 liter of per minute, and thermal degradation at 400 ℃, makes metallic iron powder, further grinding, screening, classification, can obtain granularity at the following superfine metal iron powder of 200 order product.
Gained metallic iron powder is got to 0.5 gram, mix with 500 milliliters of 10PPM dye concentration methylene blue waste water, drip 10 milliliters of hydrogen peroxide, and drip 5 milliliters of 0.5M sulphuric acid solns, stir after 20 minutes and filter, can obtain clarifying colourless solution.
Embodiment 2
Adopt the technological principle of " leach-absorption deironing-extracting and enriching valuable metal-electrodeposition " as shown in Figure 1, get certain low-grade copper breeze (80 orders sieve), calcining after high-temperature roasting, getting 1 kilogram mixes with the dilute sulphuric acid of 10 liters of 0.2M, and after being heated to 80 degrees Celsius, keep agitation leach reaction after 1 hour, and with calcining regulator solution pH, be 2.3 left and right, then filter and obtain clear filtrate, about iron content 3.5g/L wherein, the about 0.6g/L of cupric.
Get this clarification immersion liquid, drop into 200 grams of garlic slag adsorbents, stirring reaction, after 100 minutes, filters and collects filtrate, and recording concentration of iron remaining in filtrate is 0.11g/L, copper 0.58g/L, and this filtrate adopts extraction agent P again
204with solution contact reacts, extraction cupric ion wherein, and obtain through washing, back extraction the copper solutions that concentration is 17.8g/L, further extracting-back extraction makes its concentration be increased to 53g/L after processing, and can supply with galvanic deposit operation and reclaim copper metal wherein.
Adsorbed the sorbent material of iron with after distilled water wash 3 times, the baking oven hot blast of putting into 60 ℃ dries 6 hours; The dry sorbent material of gained is put into porcelain boat tiling and open, put into tube furnace, keeping vacuum tightness is 100 handkerchiefs, thermal degradation at 400 ℃, make metallic iron powder, further grinding, screening, classification, can obtain granularity at the following superfine metal iron powder of 200 order product.
Gained metallic iron powder is got to 5.5 grams, with the concentration of 500 milliliters of artificial preparations be 10PPM containing cadmium heavy metal aqueous solution, stirs filtration after 4 hours, in filtrate, residual concentration of cadmium ions is 0.1PPM.
Embodiment 3
Adopt the technological principle of " leach-absorption deironing-extracting and enriching valuable metal-electrodeposition " as shown in Figure 1, get the acid waste water of certain stope, wherein, about iron content 1g/L, about cupric 0.15g/L, pH is 2.5.
Get 1 liter of this immersion liquid, drop into 100 grams of garlic slag adsorbents, stirring reaction, after 120 minutes, filters, and it is 0.05g/L that the filtrate that filtration is collected records wherein remaining concentration of iron, and copper 0.15g/L, adopts extraction agent P again by this solution
204with solution contact reacts, extraction cupric ion wherein, and obtain through washing, back extraction the copper solutions that concentration is 28g/L, can supply with galvanic deposit operation and reclaim copper metal wherein.
To adsorb the dry sorbent material of iron gained with after distilled water wash 3 times, the baking oven hot blast of putting into 60 ℃ dries 6 hours; The dry sorbent material of gained is put into porcelain boat tiling and is opened, and puts into tube furnace, passes into nitrogen, nitrogen flow rate is 0.1 liter of per minute, and thermal degradation at 500 ℃, can make metallic iron powder, further grinding, screening, classification, can obtain granularity at the following superfine metal iron powder of 200 order product.
Gained metallic iron powder is got to 1 gram, mix with 500 milliliters of 10PPM dye concentration Methyl Orange in Wastewaters, drip 10 milliliters of hydrogen peroxide, and drip 5 milliliters of 0.5M sulphuric acid solns, stir after 30 minutes and filter, can obtain clarifying colourless solution.
Embodiment 4
Adopt the technological principle of " leach-absorption deironing-extracting and enriching valuable metal-electrodeposition " as shown in Figure 1, get certain low ore grade nickel breeze (150 orders sieve), getting 1 kilogram mixes with the dilute sulphuric acid of 8 liters of 0.2M, and after being heated to 80 degrees Celsius, keep agitation leach reaction after 1 hour, with breeze regulator solution pH, be 2.3 left and right, then filter and obtain clear filtrate, iron content 5.5g/L left and right wherein, nickeliferous about 1.3g/L.
Get this clarification immersion liquid, drop into 350 grams of garlic slag adsorbents, stirring reaction, after 300 minutes, filters and collects filtrate, and recording concentration of iron remaining in filtrate is 0.2g/L, nickel 1.25g/L, and this filtrate adopts P again
204with solution contact reacts, extraction nickel ion wherein, and obtain through washing, back extraction the nickel solution that concentration is 10.8g/L, can supply with galvanic deposit operation and reclaim nickel metal wherein.
And the sorbent material that has adsorbed iron is with after distilled water wash 3 times, the baking oven hot blast of putting into 60 ℃ dries 6 hours; The dry sorbent material of gained is put into porcelain boat tiling and open, put into tube furnace, logical argon shield, thermal degradation at 400 ℃, makes metallic iron powder, and further grinding, screening, classification, can obtain granularity at the following superfine metal iron powder of 200 order product.
Gained metallic iron powder is got to 5 grams, and the cupric heavy metal aqueous solution with 500 milliliters of artificial concentration of preparing are 10PPM, stirred after 4 hours, and in solution, residual copper ion concentration is 0.3PPM.
Embodiment 5
Adopt the technological principle of " leach-absorption deironing-adsorption and enrichment valuable metal-electrodeposition " as shown in Figure 1, get certain low-grade cobalt-containing metallurgical slag (100 orders sieve), getting 1 kilogram mixes with the dilute sulphuric acid of 10 liters of 0.3M, and after being heated to 80 degrees Celsius, keep agitation leach reaction after 1 hour, with metallurgical slag powder regulator solution, pH is 2.3 left and right, then filter and obtain clear filtrate, wherein iron content 5.5g/L left and right, contains the about 0.3g/L of cobalt.
Get this clarification immersion liquid, drop into 450 grams of garlic slag adsorbents, after stirring reaction 300 minutes, filter and collect filtrate, recording concentration of iron remaining in filtrate is 0.2g/L, cobalt 0.25g/L, this filtrate adopts 300 Keshan bamboo slags and solution contact reacts again, adsorbing and extracting cobalt ion wherein, and obtain through washing, desorb the cobalt liquor that concentration is 3.8g/L, can supply with galvanic deposit operation and reclaim cobalt metal wherein.
And the sorbent material that has adsorbed iron is with after distilled water wash 3 times, the baking oven hot blast of putting into 60 ℃ dries 6 hours; The dry sorbent material of gained is put into porcelain boat tiling and opens, put into tube furnace, under vacuum condition at 400 ℃ thermal degradation, make metallic iron powder, further grinding, screening, classification, can obtain granularity at the following superfine metal iron powder of 200 order product.
Gained metallic iron powder is got to 5 grams, and the mercurous heavy metal aqueous solution with 500 milliliters of artificial concentration of preparing are 1PPM, stirred after 4 hours, and in solution, residual ion concentration of mercury is 0.003PPM.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of principle of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes, is characterized in that: this processing step is as follows:
First, get iron content and valuable metal Zn, Cu, Ni, Co, In, the low-grade valuable metals breeze pickling liquor of Bi or containing Fe and valuable metal Zn, Cu, Ni, Co, In, the acid waste water of Bi, by adding metal mining powder of the same race, regulating the pH value of pickling liquor or acid waste water is 2～3, add biomass absorbent agent material, the addition of biomass absorbent agent material is that every liter of pickling liquor or waste water add 0.1～300g, stirring reaction 100～300min, filter, obtain being enriched with the biomass adsorbent powder of trivalent metal iron ion and the filtrate of being rich in other valuable metals,
Then, be rich in filtrate and the extraction agent of valuable metal, as P
204contact, extraction valuable metal ions wherein, obtains through washing, back extraction the solution that contains valuable metal, supplies with electrodeposition operation and reclaims valuable metal wherein; Or being rich in filtrate and the biomass adsorbent contact reacts of valuable metal, absorption valuable metal ions wherein, obtains through washing, desorb the solution that contains valuable metal, supplies with electrodeposition operation and reclaims valuable metal wherein;
Finally; be enriched with the biomass adsorbent powder of trivalent metal iron ion after distilled water repetitive scrubbing 2～3 times; put into the baking oven hot-air seasoning 6～8h of 60～80 ℃; the dry absorbent powder of gained is laid in porcelain boat, puts into tube furnace, in vacuum, pass under the condition of protective gas or reactive gas; thermal degradation at the temperature of 400～600 ℃; make metallic iron powder, then pass through grinding, screening, classification, obtain the superfine metal iron powder of granularity below 200 orders.
2. low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes according to claim 1, it is characterized in that: prepared superfine metal iron powder is 1 gram according to mass volume ratio: the ratio of 0.1-10 milliliter hydrogen peroxide, the pH of regulator solution is in 1～6 scope, carry out stirring reaction, preparation obtains having the Fenton's reaction system of strong oxidation capacity, for improvement and the purifying treatment of trade effluent.
3. low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes according to claim 1, is characterized in that: the grade of low-grade valuable metals is below 1%.
4. low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes according to claim 1, is characterized in that: the protective gas passing in tube furnace is hydrogen, argon gas, nitrogen, carbonic acid gas, and reactive gas is air.
5. low grade ore valuable metal leaching-biological adsorption-electrodeposition hydrometallurgical processes according to claim 1, is characterized in that: the preparation method of described biomass absorbent agent material is: by contain-COOH ,-SH ,-NH after washing
2,-(phenol) biomass of OH active function group, as garlic slag, mangosteen slag, marine alga, vinasse, tangerine slag, Pericarpium Mali pumilae, pomelo peel are uniformly mixed and react according to the mass ratio of 1:0.05-0.2:0.5-2 with alkali, water, stir 12～24 hours, filter, obtain solid product, wherein, described alkali is oxide compound, oxyhydroxide, carbonate, supercarbonate or volatile salt, bicarbonate of ammonia, the urea of lithium, sodium, potassium, calcium, magnesium, one or two or more kinds mixing in ammoniacal liquor; Above solid product is washed with water until neutral, send into vacuum drying oven, temperature be 60～120 ℃ dry, ovens dry thing is smashed, is sieved, the following particle collection of 40 order obtains biomass absorbent agent material.
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| CN106222422A (en) * | 2016-08-22 | 2016-12-14 | 南昌航空大学 | A kind of rich in heavy metal biological precipitation slag short route metal smelt recovery new method |
| CN107779597A (en) * | 2017-10-11 | 2018-03-09 | 大连理工大学 | A kind of method using biomass solution iron purification |
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| CN103397190A (en) * | 2013-07-29 | 2013-11-20 | 紫金矿业集团股份有限公司 | Method for producing high-purity gold and copper sulphate from gold-bearing copper sludge |
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| CN1730683A (en) * | 2005-08-25 | 2006-02-08 | 株洲冶炼集团有限责任公司 | High Iron zinc calcine process method |
| CN1837380A (en) * | 2006-04-18 | 2006-09-27 | 祥云县飞龙实业有限责任公司 | Wet-method process for reclaiming zinc from zinc leaching residue |
| WO2009026682A1 (en) * | 2007-08-28 | 2009-03-05 | Vale Inco Limited | Resin-in-leach process to recover nickel and/or cobalt in ore leaching pulps |
| CN101545050A (en) * | 2009-04-30 | 2009-09-30 | 中南大学 | A method to comprehensively recover the solid material containing copper and vanadium |
| CN102061382A (en) * | 2011-01-11 | 2011-05-18 | 昆明理工大学 | Method for recycling zinc from zinc leaching slag cleaning solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106222422A (en) * | 2016-08-22 | 2016-12-14 | 南昌航空大学 | A kind of rich in heavy metal biological precipitation slag short route metal smelt recovery new method |
| CN107779597A (en) * | 2017-10-11 | 2018-03-09 | 大连理工大学 | A kind of method using biomass solution iron purification |
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| CN104060091B (en) | 2016-02-24 |
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