CN110846510A - Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid - Google Patents

Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid Download PDF

Info

Publication number
CN110846510A
CN110846510A CN201911317637.2A CN201911317637A CN110846510A CN 110846510 A CN110846510 A CN 110846510A CN 201911317637 A CN201911317637 A CN 201911317637A CN 110846510 A CN110846510 A CN 110846510A
Authority
CN
China
Prior art keywords
mercury
rhenium
waste acid
adsorption
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911317637.2A
Other languages
Chinese (zh)
Other versions
CN110846510B (en
Inventor
张福元
徐娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University of Technology AHUT
Original Assignee
Anhui University of Technology AHUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui University of Technology AHUT filed Critical Anhui University of Technology AHUT
Priority to CN201911317637.2A priority Critical patent/CN110846510B/en
Publication of CN110846510A publication Critical patent/CN110846510A/en
Application granted granted Critical
Publication of CN110846510B publication Critical patent/CN110846510B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B43/00—Obtaining mercury
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

The invention discloses a method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid, belonging to the technical field of comprehensive recovery of rare and precious metals. The process comprises the steps of pretreatment of resin, pretreatment of multi-element mixed waste acid, synergistic co-adsorption of rhenium and mercury in the multi-element mixed waste acid and desorption of rhenium and mercury rich in resin. According to the invention, rhenium and mercury are selectively and efficiently adsorbed and recovered from the copper smelting multi-component mixed waste acid by adopting the weakly alkaline chelating anion exchange resin, and the specific process is optimized, so that rhenium and mercury in the multi-component mixed waste acid can be respectively recovered, the recovery effect of rhenium and mercury is effectively improved, the recovery of rare metal rhenium and the enrichment of harmful element mercury in the copper smelting industry are realized, the subsequent production of rhenium and mercury related products are facilitated, and meanwhile, the process is simple, short in flow, high in product purity, small in pollution, low in cost and easy to industrialize.

Description

Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid
Technical Field
The invention belongs to the technical field of comprehensive recovery of rare and precious metals, and particularly relates to a novel method for simultaneously and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid by adopting anion exchange resin.
Background
Rhenium is one of seven rare dispersed metals, and the abundance in the earth crust is only 10-8%, is trueA metal in a dispersed state. Rhenium has a high melting point next to tungsten, up to 3170 ℃, a boiling point of up to 5900 ℃, and a density next to that of the heavy platinum group metals, up to 21.02g/cm3The high melting point, the high corrosion resistance and the extremely strong plasticity of rhenium enable the rhenium to form an alloy material with excellent performance and a rhenium effect with various transition metals, so the rhenium has special and key application in the aspects of manufacturing of aeroengine turbine blades, nuclear reactor alloys, missile high-temperature parts, special crucibles, over-temperature materials and the like. Meanwhile, the 4d electronic layer of unsaturated rhenium is easy to give 5 electrons and has larger lattice parameters, so that rhenium and compounds thereof have special catalytic performance and irreplaceable application in the field of petroleum catalysts; in addition, rhenium has important applications in special coatings, the electronics industry, biological activity, and the like. Therefore, the recovery and utilization of rhenium are of great significance.
However, rhenium is difficult to form into developmentally valuable independent deposits, which are thiophilic with molybdenum, and ReS2And MoS2Have the same sheet crystal structure, so that they often enter the molybdenite lattice like a quality and accompany molybdenum; meanwhile, rhenium and copper have similar ionic radii and very similar chemical properties, so rhenium often enters chalcocite in a similar manner, and therefore, molybdenum concentrate, copper concentrate and copper-molybdenum concentrate are main raw materials for recovering rhenium. China is the largest molybdenum producing country in the world, and the yield of molybdenum reaches 23360 tons in the first quarter of 2019, which accounts for 37 percent of the global yield; meanwhile, the yield of refined copper in China is always stable in the world for many years, and in 2018, the yield of refined copper reaches 860 ten thousand tons, wherein about 80 percent of refined copper is smelted by a pyrogenic process. In the pyrometallurgical process of molybdenum and copper, most of rhenium is oxidized and volatilized and then enters SO2In the purification and washing wastewater, the wastewater is industrially called as waste acid or waste acid, and contains various anions, which can be called as multi-element mixed waste acid, so the copper and molybdenum smelting waste acid becomes the main raw material source for recovering rhenium at present.
Statistical data show that about 0.7 ton of waste acid is generated in the pyrometallurgical smelting of 1 ton of metal molybdenum, about 1 ton of waste acid is generated in the pyrometallurgical smelting of 1 ton of copper, the rhenium content in the molybdenum smelting waste acid is high and can reach 200-300ppm, and the rhenium content in the copper smelting waste acid is only a few ppm and can reach hundreds of ppm. The annual molybdenum smelting production waste acid in China is about 1.6 ten thousand tons, and the average rhenium content is about 5.0 tons; and the annual waste acid produced in copper smelting is about 700 ten thousand tons, and the rhenium content reaches 70 tons every year according to the rhenium content of 10 ppm. Therefore, copper smelting waste acid is a main raw material source of rhenium, and smelting enterprises capable of recovering rhenium in China always report that the metal rhenium yield is only 3-5t, so that huge rhenium resource waste is caused.
In the pyrometallurgical process of copper, due to the high-temperature oxidation effect, various low-melting-point and volatile elements enter purified waste acid, so that the waste acid has complex components, such as various valuable and toxic and harmful elements containing copper, lead, zinc, mercury, selenium, fluorine, chlorine, arsenic, rhenium, thallium and the like. The sulfur in the waste acid is mainly H2SO4And SO2H formed by dissolving in water2SO3In which H is2SO3The component accounts for more than 60 percent of the total S; containing both H3AsO3And H3AsO4，H3AsO3More than 80% of the total As, and HCl, HF and HReO4And inorganic acids with various elements and different valence states are typical 'multi-element mixed waste acid'. At present, a process for separately recovering rhenium is provided for copper smelting waste acid, a method for recovering mercury in the copper smelting waste acid is just described, and a method for simultaneously enriching rhenium and mercury in a complex system of multi-element mixed waste acid is provided.
Mercury is used as the only liquid metal, the application of the mercury is mainly in the aspects of manufacturing chemical agents, electronic device components and the like, a common application is a thermometer, the application field of the mercury is much smaller than that of rhenium, the mercury has high toxicity, the highest value of the national permitted wastewater discharge standard is only 0.05ppm, and the mercury is the most strict discharge pollutant. In the prior art, relevant researches on the adsorption and removal of harmful element mercury have been carried out, for example, Yan morning glory (201110379128.X) removes mercury from by-product hydrochloric acid in a tap water tower produced by calcium carbide method polyvinyl chloride or waste acid in a hydrochloric acid resolving system and waste water from an alkaline washing tower, and adopts ion exchange resin (AMBERSEP) with a sulfhydryl functional group or a thiourea functional groupTMMR10) for mercury adsorption. It is directed to a system of "chloride ion" system, the main anionThe ion being Cl-Main anion SO of waste acid mixed with copper smelting4 2-The resin has obvious difference, and the resin only has adsorption effect on mercury, and selective adsorption of rhenium or simultaneous high-efficiency co-adsorption of rhenium and mercury still remains the biggest difficulty in the industry.
In the prior art, methods for recovering rhenium from copper smelting waste acid mainly comprise a solvent extraction method, a chemical precipitation method and an ion exchange method. The solvent extraction method mainly comprises the steps of selectively extracting rhenium from waste acid or other rhenium-containing solutions by using extracting agents such as amine, ketone, alcohol, ether and ester, and in order to improve the extraction efficiency, a centrifugal extraction device is adopted by Zhang Mannman (mining and metallurgy, 2018,27(6):75-79) to recover rhenium from copper smelting waste acid, the extraction process has the advantages of mild condition, high recovery speed and the like, but the defects of easy volatilization, flammability and explosiveness of organic matter extracting agents and diluents, high requirement on solid content of feed liquid, easiness in generation of third phase, overproof organic matters in the extracted waste acid, overproof organic matters in ammonium rhenate products and the like exist, particularly hundreds of tons of waste acid produced by copper smelting enterprises per day is low in acid content, thousands of the extracted waste acid is high in infrastructure scale, the occupied area is wide, and the cost is high.
The chemical precipitation method for enriching rhenium from waste acid mainly utilizes the reduction-precipitation principle, firstly reduces high-valence rhenium in the waste acid into low-valence rhenium, then adopts the vulcanization precipitation principle to carry out precipitation enrichment on the low-valence rhenium to obtain rhenium-rich slag, so that rhenium in the waste acid is enriched. The commonly used precipitator is mainly sodium thiosulfate, impurity ions such As As and Cu can be partially co-precipitated into the rhenium-rich slag in the process, and particularly, the sodium thiosulfate can be combined with H in waste acid in the rhenium precipitation process2SO3The sulfur generated by disproportionation reaction enters the rhenium-rich slag, thereby bringing great difficulty to the leaching of rhenium in the rhenium-rich slag in the later period. Meanwhile, the precipitation method is more suitable for enriching rhenium in a system with higher rhenium content, and even if the formed precipitate at the ppm level has low solid content in the solution, the rhenium loss caused by solid-liquid separation is not easy to occur.
The ion exchange method is to adopt special ion exchange resin to exchange, adsorb and separate target ions in the solution, and the process has the advantages of short flow, simple and convenient operation, easy large-scale production and the like, so related researchers have researched and adopted the ion exchange resin to recover rhenium in the copper smelting waste acid in recent years.
For example, Zhang Bo (201710434010.X) adopts composite amino ethylene series weak-alkaline anion resin to recover rhenium in copper smelting waste acid, which mainly aims at recovering rhenium with low concentration of 2-10ppm, and harmful element arsenic basically does not influence the process, so that rhenium-rich liquid with the content of 0.9-3.2g/LRe can be recovered; chenkunkun (201610250762.6) adopts strong-base ion exchange resin to simultaneously adsorb 10-1000mg/L Re and 10-100mg/L Bi in the acidic wastewater, and then respectively analyzes Re and Bi to obtain a rhenium-rich liquid and a bismuth-rich liquid; zhang Ping (201910098339.2) uses bromine water to oxidize thallium in the smelting plant wastewater to high valence, then uses macroporous anion resin to adsorb rhenium and thallium at the same time, the recovery rate of thallium is 83.4% -85.7%, the recovery rate of rhenium is 82.2% -86.6%, but the process introduces bromine water to oxidize Tl+And Tl+Oxidation to Tl3+The standard electrode potential of (1.25) is difficult to realize in a solution containing a large amount of sulfurous acid and arsenous acid, and the introduction of bromine increases a new pollution source; wangshengli (201810703329.2) adopts commercial macroporous anion exchange resin to extract rhenium from copper smelting waste acid, and the rhenium content in the waste acid is mainly 2.89-21.25 mg/L.
However, in the existing research, when the rhenium in the waste acid is recovered by adopting an ion exchange method, only the adsorption performance and effect of the rhenium as a target element are basically considered, and the influence of mercury is not considered. Because a small amount of mercury existing in copper smelting waste acid exists in a complex anion form, ion exchange resin inevitably adsorbs partial mercury complex anions in waste acid in the process of adsorbing a target element rhenium, and partial mercury is also jointly analyzed along with rhenium in the analysis process of the target element rhenium, so that rhenium-rich liquid contains certain mercury ions, the rhenium-rich liquid is polluted, on one hand, part of mercury ions volatilize in the evaporation and concentration process of the rhenium-rich liquid, and most of mercury ions remain in the concentrated solution, so that high-purity ammonium rhenate (the content of more than 99.9%) is difficult to produce, on the other hand, the toxicity of evaporated mercury is high, and the mercury becomes a serious pollution source.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects existing in the prior method for recovering rhenium from the copper smelting multi-element mixed waste acid, and provides a method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting multi-element mixed waste acid. By adopting the technical scheme of the invention, rhenium and mercury in the copper smelting multi-element mixed waste acid can be respectively recovered, the influence of mercury in the waste acid on the recovery of rhenium is effectively avoided, and the recovery effect of rhenium is obviously improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-component mixed waste acid, which takes weak-base chelating anion exchange resin as an adsorbent to adsorb the copper smelting multi-component mixed waste acid to recover rhenium and mercury, and specifically comprises the following steps:
step one, pretreatment of resin
Firstly, soaking macroporous weakly-alkaline chelating anion exchange resin in water to perform swelling treatment, and then sequentially performing washing, alkaline soaking conversion, washing and acid soaking conversion treatment;
step two, pretreatment of the multielement mixed waste acid
Adding a flocculating agent into the to-be-treated multi-element mixed waste acid for flocculation and sedimentation treatment, and then filtering to obtain qualified multi-element mixed waste acid;
step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Enabling the pretreated polybasic mixed waste acid to pass through an adsorption column from top to bottom, and adsorbing rhenium and mercury in the polybasic mixed waste acid by using the anion exchange resin obtained in the step one in the adsorption column;
step four, resolving rhenium and mercury rich in resin
And respectively adopting a rhenium analysis agent and a mercury analysis agent to carry out analysis treatment on the resin after adsorption treatment to obtain a rhenium-containing analysis liquid and a mercury-containing analysis liquid, namely realizing efficient recovery of rhenium and mercury in the copper smelting multi-element mixed waste acid.
Further, the macroporous weakly basic chelating anion exchange resin is D304 type resin.
Furthermore, tap water, softened water or circulating water of copper smelting enterprises is adopted as water for the water immersion swelling treatment in the step one, and the treatment time is 10-30 hours, preferably 24 hours; the alkali used in alkaline leaching transformation is NaOH, KOH or NH4One or more than one of OH, the mass concentration of the OH is 0.1-20%, preferably 5-10%, the pH of the solution after alkaline leaching transformation is 12-14, and the time of alkaline leaching transformation treatment is 2-30h, preferably 24 h.
Furthermore, in the step one, the acid used for acid leaching transformation is single acid, a multiple mixed acid is prepared or multiple mixed waste acid for copper smelting is prepared, the pH value is less than 1, the mass concentration of the acid is 2-20%, preferably 2-5%, and the acid leaching transformation treatment time is 2-30h, preferably 24 h.
Furthermore, in the second step, a polyacrylamide product is used as the flocculant, preferably a zwitterionic carboxyl-type polyacrylamide flocculant, and the addition amount of the flocculant is one ten-thousandth to ten-thousandth of the waste acid to be treated.
Furthermore, in the third step, a multi-stage adsorption column is adopted to sequentially adsorb the multi-element mixed waste acid, and the adsorbed saturated resin is subjected to desorption treatment.
Furthermore, the saturation degree of the first-stage adsorption resin in the third step is 30-80%, and the saturation degree of the resin is preferably 60%; enabling the pretreated multi-element mixed waste acid to pass through a first adsorption column from top to bottom, enabling the primary adsorption tail liquid to pass through a second adsorption column, enabling the rhenium or mercury content in the secondary adsorption tail liquid to exceed a preset value, enabling the first adsorption column to be basically saturated, breaking the first adsorption column for resolution, and completing the cyclic utilization of primary resin; changing the last second adsorption column into a first adsorption column of a second cycle, wherein the second adsorption column adopts an adsorption column newly loaded with resin, the adsorption procedure of the multi-element mixed waste acid is that the tail liquid of the first adsorption enters the first adsorption column of the second cycle from top to bottom, and the tail liquid of the second adsorption passes through the second adsorption column from top to bottom, and the cycle is carried out until the content of rhenium or mercury in the tail liquid of the adsorption is lower than a preset value; and after the adsorption is finished, the content of rhenium in the adsorption tail liquid is less than 0.5ppm, the content of mercury is less than 0.01ppm, and tail liquid outlets of all stages of adsorption tail liquid are provided with sampling ports.
Furthermore, in the fourth step, the resin after adsorption treatment is washed by tap water, softened water or circulating water of copper smelting enterprises, preferably tap water; when the pH value of the effluent is less than 2, the washing speed is set to be 2-10BV, preferably 4-8 BV; when the pH value of the washing water tail liquid is 2, the flow rate of the washing water is increased to 10-30BV, preferably 15-20 BV; washing the fabric when the pH value of the effluent of the washing water is 3-7, and preferably, the pH value of the effluent of the washing water is 4.5.
Furthermore, in the fourth step, rhenium adsorbed in the resin is analyzed by using a non-soft-base rhenium analysis agent which is NaOH or Na2CO3、NaHCO3、NH4One or more OH groups with pH higher than 10 and hydroxyl concentration lower than 5mol/L, preferably 1 mol/L.
Furthermore, in the fourth step, the mercury adsorbed in the acidic mercury resolving agent resolving resin containing 'soft alkali' is adopted, and the mercury resolving agent is soft alkali salt or acid containing 'S', preferably I-、SCN-The concentration of the soluble salt of (4) is 0.1 to 1.5mol/L, preferably 0.5 to 1.0 mol/L.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-component mixed waste acid, which comprises the steps of resin pretreatment, multi-component mixed waste acid pretreatment, synergistic co-adsorption of rhenium and mercury in the multi-component mixed waste acid and desorption of rhenium and mercury in a loading-rich resin, wherein the method adopts weak-base chelating anion exchange resin to selectively and efficiently adsorb and recover rare and disperse element rhenium and harmful element mercury from the copper smelting multi-component mixed waste acid directly, and optimizes the specific process, so that rhenium and mercury in the copper smelting multi-component mixed waste acid can be respectively recovered, the recovery effect of rhenium and mercury is effectively improved, the rhenium content in the desorption solution is more than that of the mixed waste acid and is enriched by 30-500 times, the recovery of the rare and dispersed metal rhenium and the enrichment of the harmful element mercury in the copper smelting industry are effectively realized, and the production of the related products of rhenium and mercury is facilitated, meanwhile, the method has the advantages of simple process, short flow, high product purity, little pollution, low cost and easy industrialization.
(2) According to the method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting multi-component mixed waste acid, the D304 type resin with high selectivity is adopted to simultaneously adsorb and recover rhenium and mercury in the copper smelting multi-component mixed waste acid, so that the rhenium and mercury in the waste acid do not form a competitive relationship on the process of adsorbing rhenium and mercury by resin, mercury remaining in the waste acid is effectively adsorbed while rhenium is adsorbed and recovered by resin, the rhenium content in tail liquid is reduced to 0.5ppm, and mercury is reduced to 0.01ppm, so that the influence of mercury in the waste acid on the recovery of rhenium is effectively avoided, the recovery effect of rhenium is improved, and the effective control of harmful element mercury is realized. Meanwhile, the selected resin has strong anti-fouling capability, high adsorption capacity and long service life, and the adsorption and desorption capability of the resin which is recycled for 330 days in industrial experiments is not obviously weakened, so that the adsorption effect is good.
(3) According to the method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting multi-element mixed waste acid, the specific process parameters are optimized, so that the recovery effect of rhenium and mercury is further improved, and the pollution of mercury is reduced. Meanwhile, the rhenium and mercury analytic agents adopted in the step four are respectively optimized and selected, so that on one hand, rhenium and mercury can be fully separated, the analytic efficiency is improved, impurity ions in rhenium analytic solution are few, the production of the subsequent rhenium related products is facilitated, on the other hand, mercury can be fully analyzed, the phenomenon that the exchange capacity of resin is reduced or the service life of the resin is shortened due to resin poisoning caused by the fact that a large number of colloidal fine mercury particles enter resin micropores is avoided, the original adsorption performance is lost, and the rhenium and mercury analytic solutions are cheap, easy to obtain, non-toxic, harmless, small in mutual pollution and basically free of reduction of the cyclic utilization capacity of the resin. In addition, the invention effectively fills the technical blank of simultaneously adsorbing rhenium and mercury in the copper smelting multi-component mixed waste acid in the prior art, does not generate new pollutants in the whole process, does not change the main components in the copper smelting multi-component mixed waste acid, and does not influence the waste acid treatment process flow of smelting enterprises.
Detailed Description
In the prior art, when the ion exchange method is adopted to recycle rhenium in the copper smelting multielement mixed waste acid, only the adsorption performance and effect of the target element rhenium are basically considered, the influence of mercury is not considered, the ion exchange resin can inevitably adsorb partial mercury complex anions in waste acid in the process of adsorbing the target element rhenium, and partial mercury can be jointly desorbed along with rhenium in the process of desorbing rhenium, thereby influencing the absorption and recovery of the rhenium element, leading the rhenium-rich liquid to contain certain mercury ions and polluting the rhenium-rich liquid, on one hand, part of the mercury ions volatilize in the evaporation and concentration process of the rhenium-rich liquid, most mercury ions remain in the concentrated solution, which reduces the purity of the rhenium-rich solution, so that high-purity ammonium rhenate (with the content of more than 99.9%) is difficult to produce, and on the other hand, the evaporated mercury also becomes a serious pollution source.
Meanwhile, in the prior art, when the common anion exchange resin is adopted to adsorb rhenium in the waste acid, only part of mercury is adsorbed, and most of mercury remains in the adsorbed liquid of the waste acid, so that mercury with low concentration originally is further dispersed in a solid-liquid two-phase state, and the comprehensive treatment of mercury pollution is very unfavorable; in addition, after the common resin absorbs part of mercury, only a small part of mercury is analyzed in the process of analyzing rhenium, so that the exchange capacity of the resin is reduced or the service life of the resin is shortened, and a large number of colloidal fine mercury particles enter resin micropores to cause resin poisoning, so that the original adsorption performance is lost.
Based on the situation, the invention provides a method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-component mixed waste acid, which comprises the steps of pretreatment of resin, pretreatment of the multi-component mixed waste acid, synergistic co-adsorption of rhenium and mercury in the multi-component mixed waste acid and desorption of rhenium and mercury in the rich-loading resin. According to the invention, the weakly alkaline chelating anion exchange resin is adopted to directly and efficiently adsorb and recover the scattered element rhenium and the harmful element mercury from the copper smelting multi-element mixed waste acid selectively, namely the D304 type resin with high selectivity is adopted to simultaneously adsorb and recover the rhenium and the mercury in the copper smelting multi-element mixed waste acid, so that the rhenium and the mercury in the waste acid are not in a competitive relationship with the resin in the process of adsorbing rhenium and mercury, the mercury remained in the waste acid is effectively adsorbed while the rhenium is adsorbed and recovered by the resin, the rhenium content in the tail liquid is reduced to 0.5ppm, and the mercury is reduced to 0.01ppm, thereby effectively avoiding the influence of the mercury in the waste acid on the recovery of rhenium, improving the recovery effect of rhenium, realizing the effective control of the harmful element mercury, effectively adsorbing, recovering and resolving the mercury in the waste acid, improving the exchange capacity of the resin and prolonging the service life of the resin, and avoiding the resin poisoning caused by a large amount of colloidal fine mercury particles entering resin micropores, thereby losing the original resin And (4) adsorption performance. Meanwhile, the selected resin has strong anti-fouling capability, high adsorption capacity and long service life, and the adsorption and desorption capability of the resin which is recycled for 330 days in industrial experiments is not obviously weakened, so that the adsorption effect is good.
In addition, the invention also carries out optimization design on specific process parameters when carrying out the adsorption recovery of rhenium and mercury, thereby further improving the recovery effect of rhenium and mercury and reducing the pollution of mercury. The invention also optimizes and selects the rhenium and mercury analytic agents adopted in the step four respectively, so that on one hand, rhenium and mercury can be fully separated, the analytic efficiency is improved, impurity ions in the rhenium analytic solution are few, the production of the subsequent rhenium related products is facilitated, on the other hand, mercury can be fully analyzed, the phenomenon that the exchange capacity of the resin is reduced or the service life of the resin is shortened due to resin poisoning caused by the fact that a large number of colloidal fine mercury particles enter resin micropores is further avoided, the original adsorption performance is lost, and the rhenium and mercury analytic solutions are cheap and easy to obtain, non-toxic and harmless, small in mutual pollution, and the cyclic utilization capacity of the resin is basically not reduced. In addition, the invention effectively fills the technical blank of simultaneously adsorbing rhenium and mercury in the copper smelting multi-component mixed waste acid in the prior art, does not generate new pollutants in the whole process, does not change the main components in the copper smelting multi-component mixed waste acid, and does not influence the waste acid treatment process flow of smelting enterprises.
Specifically, the method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting multi-component mixed waste acid, disclosed by the invention, uses weak-base chelating anion exchange resin as an adsorbent to adsorb and treat the copper smelting multi-component mixed waste acid to recover rhenium and mercury, and specifically comprises the following steps of:
step one, pretreatment of resin
The macroporous weakly-alkaline chelating anion exchange resin is firstly subjected to water immersion swelling treatment by using tap water, softened water or circulating water of copper smelting enterprises, a water source without complex anions is preferred, the water immersion swelling treatment time is generally static immersion for 10-30h, preferably 24h, and the fact that the leaching cost can be effectively reduced by using the tap water or the circulating water of the copper smelting enterprises is worth explaining. After swelling, washing the resin by using tap water, softened water or circulating water of copper smelting enterprises without complex anions so as to remove soluble acidic, alkaline and soluble substances, wherein the washing end point is that the pH of the effluent of washing water is about 7, and no suspended matters or solid impurities are observed by eyes; then, carrying out alkaline leaching transformation by adopting an alkaline solution with a certain mass concentration, and washing the resin to be neutral by adopting a water washing process after the transformation is finished; then adopting single acid, preparing multi-component mixed acid or copper smelting multi-component mixed waste acid to carry out acid leaching transformation, and adopting a water washing process to wash the resin to be slightly acidic after the transformation is finished.
The macroporous weakly basic chelating anion exchange resin in the step one is D304 type resin, and the weakly basic group of the macroporous weakly basic chelating anion exchange resin can react with ReO4 -Ions are selectively exchanged while other anions such as: SO (SO)4 2-、SO3 2-、F-、Cl-The anions have no adsorption effect, and the arsenic in the multielement mixed waste acid is mostly As3+In the form of and containing a small amount of As5+And +3 valent As may form AsO3 3-、HAsO3 2-And H2AsO3 -The anions in multiple valence states need to exist in a strong alkaline environment, and almost 100 percent of the As with the valence of 3 in an acidic environment is neutral H3AsO3In the form of As3+Does not influence the adsorption of rhenium on the anion resin;the +5 As is required to form AsO in a strongly alkaline environment4 3-、HAsO4 2-Anion, with H at pH equal to 23AsO4And H2AsO4 -Forms coexist, with pH less than 2 being predominantly H3AsO4Form exists so that5+Adsorption of ReO to anionic resins4 -The ions have substantially no effect. And the mercury is in the valence of +1 or +2 in the multi-element mixed waste acid, belongs to weak acid substances, and can be selectively adsorbed and recovered by chelating with the S of soft alkali, so that the aim of simultaneously adsorbing rhenium and mercury by the resin is fulfilled. The D304 type resin adopted in the invention not only has a functional group for exchanging rhenium anions, but also has a chelating functional group, and mercury can be adsorbed no matter what valence state is according to the 'soft and hard acid-base theory'.
The alkali used in the alkali leaching transformation in the first step is alkali without other non-hydroxide anions, namely the alkali solution is NaOH, KOH or NH4One or more OH groups are combined, and the mass concentration of the OH groups is 0.1-20%, preferably 5-10%. It is worth to be noted that the lower alkali concentration makes the residual alkali amount of the solution after transformation less, which is beneficial to saving alkali cost, and meanwhile, the lower alkali concentration also needs to ensure that the solution is strongly alkaline in the transformation process; higher alkali concentrations result in faster resin transformation rates, but excess alkali remains in the solution after transformation, increasing processing costs. The treatment time of the alkali leaching transformation process is 2-30h, preferably 24h, the pH of the solution after the alkali leaching transformation is 12-14, the alkali leaching transformation can be carried out by adding a small amount of alkali in batches, the alkali consumption is reduced, and the water washing of the next process after the alkali leaching transformation is facilitated.
When single acid is adopted, multiple mixed acid is prepared or multiple mixed waste acid for copper smelting is adopted for acid leaching transformation in the step one, the single acid is HCl and H2SO4And one of HF and HCl and H as polybasic mixed acid2SO4And two or more of HF, the acid mass concentration is 2-20%, preferably 2-5%, the acid leaching transformation treatment time is 2-30h, preferably 24h, the acid concentration requires the pH value to be less than 1, thereby avoiding the formation of anions and the shadow of the + 5-valent AsThe adsorption effect of rhenium and mercury is influenced; h is preferred for preparing the acidic solution2SO4And is preferably H2SO4The proportion of the fluorine-containing waste acid is more than 90 percent, so that impurity ions with extremely strong corrosivity such as fluorine and chlorine are prevented from entering a waste acid system; the adoption of the copper smelting multi-component mixed waste acid for acid leaching transformation is beneficial to the conversion of resin into an adsorption state and the reduction of the acid cost, so the copper smelting multi-component mixed waste acid is preferably selected for acid leaching transformation, and the washing process after the acid leaching transformation can be reduced.
Step two, pretreatment of the multielement mixed waste acid
Smelting SO with copper2The secondary dynamic wave cools and purifies the waste acid, and the waste acid is discharged after reaching the acid concentration (sulfuric acid) of 5-20% after being circulated for many times, which is worth explaining that the rhenium content in the waste acid can be accumulated through the circulation for many times, so that the rhenium content of the waste acid in unit volume is increased, and the washing and purifying cost of the sulfur dioxide dynamic wave is saved; and the concentration of sulfuric acid does not theoretically affect the adsorption of rhenium and mercury, but the concentration of sulfuric acid in the waste acid is too high, so that the viscosity of the waste acid is increased, the migration and exchange rate of rhenium, mercury and other ions is reduced, and the acidity of the copper smelting waste acid is preferably not changed. Firstly, carrying out solid-liquid separation on the discharged waste acid by a primary plate-and-frame filter press, separating more than 99% of solid insoluble substances in the waste acid to obtain acid mud and multi-component mixed waste acid, adding a small amount of flocculant into the multi-component mixed waste acid to carry out sufficient flocculation and sedimentation treatment, and then carrying out secondary filtration by using filter paper, filter membrane or filter cloth with small pore diameter to remove suspended matters, thereby obtaining qualified multi-component mixed waste acid.
The flocculant in the second step is polyacrylamide product, such as quaternary ammonium polyacrylamide, tertiary amine polyacrylamide, carboxyl polyacrylamide and amine methyl polyacrylamide, preferably zwitterionic carboxyl polyacrylamide flocculant, the addition amount of the flocculant is one ten thousandth to ten thousandth of waste acid to be treated, preferably two ten thousandth, and the reaction time is preferably more than 1 h. It is worth to say that the flocculation time is prolonged, so that the flocculation effect can be effectively increased, and the solid content in the secondary filtrate is reduced. The qualified polybasic mixed waste acid is required to have a solid content of less than 50ppm, and it is worth explaining that the lower solid content can effectively reduce the blockage of micro particles on resin particle micropores, so that the resin keeps excellent adsorption performance, and the lower solid content of particles is beneficial to improving the adsorption performance of the resin, but also increases the secondary filtration cost.
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Sequentially adsorbing rhenium and mercury in the pretreated multi-element mixed waste acid by adopting a multi-stage adsorption column, wherein anion exchange resin obtained in the step one is filled in the adsorption column, the pretreated multi-element mixed waste acid passes through a first adsorption column from top to bottom, a primary adsorption tail liquid passes through a second adsorption column from top to bottom in a pumping pressure or vacuum adsorption mode, the rhenium or mercury content in the two-time adsorption tail liquid exceeds a preset value, the first adsorption column is basically saturated, and the first adsorption column is used for desorption treatment after being disconnected, so that the cyclic utilization of the primary resin is completed; and the last second adsorption column is changed into a first adsorption column of a second cycle, the second adsorption column adopts an adsorption column which is newly loaded with resin, the adsorption procedure of the multi-element mixed waste acid is that the tail liquid of the first adsorption enters the first adsorption column of the second cycle from top to bottom, and the tail liquid of the second adsorption passes through the second adsorption column from top to bottom, and the cycle is carried out until the content of rhenium or mercury in the tail liquid of the adsorption is lower than a preset value. When the primary adsorption tail liquid enters the first adsorption column of the second cycle, the manual operation is adopted to transfer to the first adsorption column of the second cycle for secondary adsorption after the primary adsorption is finished in an experimental laboratory, and the pumping mode is adopted in industrial production to ensure that all the adsorption columns have stable and uniform flow rate.
And the secondary adsorption tail liquid in the third step passes through a second adsorption column (namely a third adsorption column) of the second cycle from top to bottom in a pumping pressure or vacuum adsorption mode, and whether third-stage adsorption is adopted or fourth-stage or fifth-stage adsorption is added in the actual control process needs to be determined according to the tail liquid condition of the previous stage. It is worth to say that when the concentration of target ions in the multi-element mixed waste acid is low (several or dozens of ppm), two-stage or three-stage adsorption is adopted, so that not only can the adsorption effect be ensured, but also the solution treatment capacity can be increased, and meanwhile, the pressure drop of each stage of adsorption can be effectively controlled, so that the previous stage of adsorption column bears smaller internal pressure, the adsorption column is protected, and the service life of the adsorption column is prolonged; when the concentration of the target ions is higher (hundreds or hundreds of ppm), four-stage or five-stage adsorption is preferably adopted, the adsorption effect of the target ions in the waste acid can be ensured as the adsorption stages are more, and the construction cost input is increased, so that the saturation degree of the first-stage adsorption resin is preferably 30-80%, and the saturation degree of the resin is more preferably 60%.
The adsorption column in the third step is preferably made of transparent glass or quartz in the laboratory experiment process, and can be made of glass fiber reinforced plastic, titanium, PPR or steel-lined plastic in the industrial production process, and the adsorption column is worthy of being explained that the glass fiber reinforced plastic or the PPR is easy to be subjected to later-stage modification, and the titanium or the steel-lined plastic is not suitable to be subjected to later-stage modification. And step three, enabling the multi-element mixed waste acid to pass through the first adsorption column from top to bottom, enabling the height of the adsorption column used in laboratory adsorption experiments to be 5-30cm, enabling the diameter of the adsorption column to have no special requirements, enabling the height of the adsorption column used in industrial production to be 1.0-4.5m, enabling the diameter of the adsorption column to be 0.5m-2.5m, and being worthy of explaining that larger diameter can be used for filling more resin, and the treatment capacity of the multi-element mixed waste acid can be increased. It is worth noting that the adsorption efficiency of rhenium and mercury in the multi-element mixed waste acid is mainly referred to the retention time of rhenium and mercury in the resin, the shorter retention time has the risk of penetration of adsorbed ions, the longer retention time can ensure the adsorption effect of adsorbed ions, and the operation efficiency of the whole system can be reduced.
The multi-element mixed waste acid in the third step passes through the first adsorption column from top to bottom, the flow rate of the multi-element mixed waste acid is 5-50BV, and the flow rate of the multi-element mixed waste acid is related to the content of adsorbed ions rhenium and mercury, and the lower content of the adsorbed ions (several ppm to dozens of ppm) can adopt higher flow rate, so that the adsorption effect can be ensured, the treatment capacity is higher, and the recovery rate and the treatment capacity are in the best state; the higher content of adsorbed ions (hundreds ppm or hundreds ppm) is preferably at a lower flow rate to ensure the adsorption efficiency of the target ions, and the final flow rate is preferably determined according to the concentration of the target ions in the first adsorption tail liquid, and the rate at which the target ions are not substantially filtered is the optimum flow rate (here, filtering means that the target ions are not completely adsorbed after the solution passes through the adsorption resin). And tail liquid outlets of all stages of tail liquid adsorption are provided with sampling ports so as to sample and test and control the flow rate of the multi-element mixed waste acid according to the concentration of all stages of tail liquid in the actual operation process. After adsorption, the content of rhenium and the content of mercury in the tail liquid are respectively less than 0.5ppm and 0.01ppm, and the lower tail liquid control standard increases the difficulty of analysis and detection, requires more precise detection equipment and increases the production cost.
Step four, resolving rhenium and mercury rich in resin
The resin which is basically saturated after adsorption treatment is washed clean by water to remove the residual multi-element mixed waste acid in the resin, then a non-soft-base rhenium analysis agent is adopted to slowly pass through the saturated resin to analyze most rhenate into solution, and mercury is continuously remained on the resin, so that high-concentration rhenium-containing analysis solution is obtained, and related products of rhenium can be directly produced after purification. And (3) after the rhenium is analyzed by the rich-loading resin, judging whether mercury analysis is carried out by directly adopting a mercury analysis agent according to the mercury adsorption capacity condition, or directly putting the rhenium into the step three after the rhenium is analyzed, and using the rhenium and mercury for co-absorption. During mercury desorption, an acidic mercury desorption agent containing soft alkali is adopted, and most of mercury is slowly desorbed to a solution through saturated resin from top to bottom, so that a mercury-containing (complex anion) solution with high concentration is obtained, mercury in the multi-element mixed waste acid is effectively controlled and enriched, rhenium and mercury in the copper smelting multi-element mixed waste acid are efficiently recovered at the same time, and the resin after mercury desorption can be used as the last-stage no-load resin of the next circulation, so that the adsorption effect of rhenium and mercury in the multi-element mixed waste acid is ensured.
In the fourth step, the water used for washing the resin after adsorption treatment is tap water, softened water or circulating water of copper smelting enterprises, and preferably tap water is used for washing. The resin washing process can be carried out by pumping tap water from top to bottom, and when the pH of the effluent of the washing water is less than 2, the slow washing water flow rate can be 2-10BV, so that the washing resin can be washed by the washing water at a low flow rate of 2-10BVObviously, the washing effect can be increased by the slower washing speed, and the risk of washing water penetration is caused by the faster washing speed, so that the washing water flow rate is preferably 4-8 BV; when the pH value of the washing water tail liquid is 2, the washing water flow rate is increased to 10-30BV, preferably 15-20BV, so As to reduce As5+The arsenic acid is dissociated into negative univalent anions to be adsorbed on the resin, so that the impurity content of the target ion solution is increased, and the subsequent purification of rhenium is more difficult; when the pH of the washing water effluent is 3-7, the washing is clean, preferably the pH of the washing water effluent is 4.5, and it is worth mentioning that the higher the pH of the washing water is, the larger the water absorption capacity is required to be, and various acids are dissociated into negative ions to be adsorbed on the resin, so that the concentration of impurity ions in the analysis solution is increased.
When the rhenium desorption agent which is not soft alkali is adopted to desorb the rhenium adsorbed in the resin in the fourth step, the rhenium desorption agent is NaOH or Na2CO3、NaHCO3、NH4One or more than one OH is/are combined, the pH value is greater than 10, the hydroxide concentration is less than 5mol/L, and the hydroxide concentration of the preferred resolving agent is 1mol/L, and it is worth to say that the lower resolving agent concentration is beneficial to separating acidic impurity ions firstly, the concentration of the rhenium-containing liquid is improved, the impurity content is reduced, and meanwhile, a larger amount of resolving agent is needed to complete the resolving of rhenium; higher concentration of the resolving liquid is easy to substitute acidic impurity ions into the resolving liquid, which is not beneficial to the separation of the early-stage impurity-containing solution. The 'soft alkali' is a classification standard of a soft and hard acid-base theory on acid-base, the flow rate of the rhenium analysis agent is 0.5-5BV, the impurity ions on the saturated resin can be separated at a proper flow rate of the analysis agent, and the analysis solution does not contain target ions at the early stage, so that the separation of the impurity ions in the analysis solution can be realized. The resin used in the invention has the desorption amount of 2-20BV, the resin with excellent performance can realize the rapid desorption of target ions, simultaneously, the desorption agent flow is prolonged to dissociate more target ions, but the target ion concentration is also reduced, therefore, the resin desorption amount is preferably 3-8BV, so that rhenium desorption solution with higher concentration can be obtained, and mercury continues to be remained on the resin.
It is worth mentioning that since the mercury content in the multi-element mixed waste acid is lower than that of rhenium, the mercury is not necessarily adsorbed and saturated after rhenium is adsorbed and saturated on the resin, so that whether mercury is desorbed can be determined according to whether the mercury concentration in the last-stage adsorption tail liquid meets the requirement when the four-stage mercury desorption is carried out, the mercury content in the tail liquid is far lower than a target value, and the rhenium is preferentially desorbed and then directly used as no-load input for adsorption. It is worth explaining that rhenium content in the last stage tail liquid firstly meets the requirement, rhenium can be analyzed firstly, the analyzed resin is used as no-load to be put into use, mercury content firstly meets the requirement, mercury can be analyzed directly according to the step four, and the analyzed resin is used as no-load to be put into use;
in the fourth step, when mercury adsorbed in the resin is analyzed, the resin after rhenium analysis needs to be washed by water to be slightly alkaline and then used for mercury analysis, the alkaline resin after rhenium analysis can be washed by water to be slightly central or directly washed by acid to be acidic, and the acid is HCl or H2SO4And one or more of HF, the concentration of acid is not more than that of the adsorption multi-element mixed waste acid, or the multi-element mixed waste acid is directly adopted to wash the resin to be close to the acidity of the multi-element mixed waste acid. When the acidic mercury resolving agent containing soft alkali is used for resolving the mercury adsorbed in the resin in the fourth step, the mercury resolving agent is mercaptan containing-SH and I-、SCN-、CN-、S2O3 2-、S2-、SO2And soft alkali salts or acids containing "S" such as sodium sulfite. It is worth mentioning that CN-、S2-Can generate extremely toxic gas in an acid environment, and is not suitable for selection; s2O3 2-The salts can react with acid to produce sulfur ions and sulfur, and are not suitable for use; under alkaline conditions S2O3 2-、S2-Easy hydrolysis or disproportionation reaction, and is not suitable for use; CN-Can be used under alkaline conditions, but CN-It is not preferable for the highly toxic substances, and therefore, it is preferable to contain I-、SCN-The concentration of the soluble salt of (4) is 0.1 to 1.5mol/L, preferably 0.5 to 1.0 mol/L. The acidity requirement of the mercury resolving agent is larger than the acidity value of the multi-element mixed waste acid, preferably 5-20%, the acid is one or the combination of two or more of sulfuric acid, hydrochloric acid, hydrofluoric acid and the like, or the multi-element mixed waste acid is directly addedThe acid is used as the base solution of the resolving agent, and can fully resolve the mercury adsorbed by the chelation on the resin to form a mercury-containing solution with higher concentration. It is worth noting that higher acidity is beneficial to increase the rate of mercury desorption.
The resolving speed of mercury on the saturated resin in the fourth step is 0.5-5BV, and it is worth explaining that the lower resolving speed can enable the resolving agent to fully play a role and increase the effect of resolving mercury; a faster resolution rate is preferred to be 2-3BV because the resolution agent may penetrate the resin, reducing the resolution efficiency. The dosage of the resolving agent is 2-15BV, preferably 3-8BV, and it is worth mentioning that the dosage of the resolving agent is less, so that the concentration of target ions in the resolving solution can be ensured, but a small amount of mercury ions can remain on the resin; the use of a large amount of the resolving agent increases the resolving power of mercury, but decreases the concentration of mercury in the resolving liquid.
The invention is further described with reference to specific examples.
Example 1
Step one, pretreatment of resin
Measuring 80ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, respectively adding 80ml of circulating water and 80ml of tap water of a copper smelting enterprise, statically soaking and swelling for 15 hours at normal temperature, pouring the mixture after swelling, removing swelling water, washing the mixture with the circulating water and the tap water in a volume ratio of 1:1 until the pH value is 7, adding 200ml of mixed alkali of KOH and ammonia water, wherein the mass concentration of the KOH is 0.2 percent, the concentration of the ammonia water is 0.1 percent, carrying out alkali leaching and transformation for 2 hours, washing the resin with the circulating water until the pH value is 7.5 after transformation is finished, carrying out acid leaching and transformation for 24 hours by using certain multicomponent mixed waste acid for copper smelting in northwest, and not washing the resin again after transformation is finished, and directly using the resin.
Step two, pretreatment of the multielement mixed waste acid
Smelting SO from northwest certain copper2The secondary dynamic wave cooling purifies waste acid by 10L, amphoteric polyacrylamide flocculant is added into the waste acid according to ten thousandths and then the waste acid is settled for 1h, the multi-component mixed waste acid is filtered in vacuum by using special replacement filter paper for commercially available gold cyanide pregnant solution, the solid content of the filtered multi-component mixed waste acid is 20ppm, and the main components are shown in the following table.
Element(s) Cu* Pb Se Cd As* F Cl Re Hg H2SO4*
Content (wt.) 3.22 —— 118 118 2.47 1902 2270 78.20 0.91 15.21
Note: unit is g/L
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
The method comprises the steps of averagely dividing pretreated 80ml of resin into 2 parts, respectively loading the 2 parts into transparent glass standard-opening adsorption columns with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption columns, slowly adding waste acid into the liquid separator, controlling the effluent of the adsorption columns to be 3.33ml/min by adjusting valves at the lower parts of the adsorption columns, controlling the adsorption rate to be about 5BV, adding effluent tail liquid into another adsorption column filled with 40ml of resin according to the steps, controlling the adsorption rate to be about 5BV, controlling the two adsorption columns to be synchronously performed, performing 500ml sampling detection on rhenium and mercury in secondary adsorption tail liquid, adsorbing 5L multielement mixed waste acid in total, wherein the rhenium content of the adsorption tail liquid after adsorption is 0.2ppm, the mercury content is 1.5ppb, the adsorption rate of rhenium is more than 99.70%, and the adsorption rate of mercury is more than 99.83.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 40ml of resin which is basically saturated in primary adsorption by softened water for one section, controlling the flow rate to be about 5BV, detecting the pH of effluent in real time, changing the pH of washing water to be about 2 when the resin is washed to 8BV into quick second-section washing, and quickly washing residual polybasic mixed waste acid in the resin to be 3.5 when the flow rate of the washing water is 15 BV; preparing 2.5mol/L sodium carbonate solution as a rhenium analysis agent, adding the solution into a washed resin adsorption column, controlling the flow rate of tail liquid to be 2BV, and analyzing the tail liquid for 3.5BV in total, wherein the first 1BV sample is returned to waste acid for re-adsorption, the rhenium content in the analysis liquid reaches 3704mg/L, 47 times of enrichment before adsorption, and the resolution reaches 95%, so as to obtain high-grade rhenium solution; and (4) returning the waste acid to the third step for reabsorption after the mercury is temporarily not resolved because the mercury content in the waste acid is lower. The resin after resolving rhenium is directly used as the last-stage no-load adsorption resin of the next cycle to carry out rhenium and mercury two-stage synergistic co-adsorption, the mercury content of the second-stage tail liquid is 2.0ppb when 4.9L of multi-element mixed waste acid is adsorbed, and the mercury adsorption rate reaches 99.78%. The adsorbed resin does not resolve rhenium, 0.5mol/L potassium iodide and 20% sulfuric acid base solution are adopted to directly resolve mercury, the resolving agent slowly passes through the saturated resin from top to bottom, the flow rate is 1BV, 3BV is resolved totally, the first 1BV returns to the solution before adsorption, the mercury content in the resolving solution is 225ppm, and the mercury is 56 times enriched compared with the previous solution.
Example 2
Step one, pretreatment of resin
Weighing 50ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, respectively adding 50ml of tap water and 50ml of softened water, statically soaking and swelling for 10 hours at normal temperature, pouring out swelling water after swelling is finished, washing the resin with the tap water to the pH value of 7, adding 100ml of mixed base of NaOH and ammonia water, wherein the mass concentration of NaOH is 2.5%, the concentration of the ammonia water is 0.5%, carrying out alkaline leaching and transformation for 5 hours, washing the resin with the tap water after transformation is finished to the pH value of 9.0, carrying out acid leaching and transformation for 8 hours by using 2.5% of mixed acid of sulfuric acid and hydrofluoric acid (the mass ratio of the sulfuric acid to the hydrofluoric acid is 9:1), and washing the tap water after transformation to the pH value of 5 for later use.
Step two, pretreatment of the multielement mixed waste acid
Taking SO of copper smelting plant in Huazhong2The second-stage dynamic wave cooling purifies 50L of waste acid, amphoteric polyacrylamide flocculant is added according to eighty-ten-thousandth of the waste acid, the waste acid is settled for 1.5h, the multi-component mixed waste acid is filtered in vacuum by using special replacement filter paper for commercially available gold cyanide pregnant solution, the solid content of the filtered multi-component mixed waste acid is 17ppm, and the main components are shown in the following table.
Element(s) Cu* Pb Se Cd As* F Cl Re Hg H2SO4*
Content (wt.) 2.13 7.70 390 —— 14.55 2710 3850 3.20 7.60 18.01
Note: unit is g/L
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
The method comprises the steps of loading pretreated 50ml of resin into a transparent glass standard port adsorption column with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption column, slowly adding waste acid into the liquid separator, controlling effluent liquid of the adsorption column to be 21ml/min by adjusting a valve at the lower part of the adsorption column, wherein the adsorption rate is about 25BV, sampling and detecting rhenium and mercury in each 500ml of effluent tail liquid, adsorbing 50L multi-element mixed waste acid in total, reducing the rhenium and mercury contents of the adsorption tail liquid to 0.1ppm and 8.5ppb respectively after adsorption, and enabling the adsorption rate of rhenium to be greater than 96.88% and the adsorption rate of mercury to be greater than 99.89%.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 50ml of resin which is basically saturated in adsorption by using tap water for one section, controlling the flow rate to be about 8BV, detecting the pH of an effluent liquid in real time, changing the pH of a washing water to be about 2 when the resin is washed to be 8BV into quick two-section washing, and quickly washing the residual polybasic mixed waste acid in the resin to be 4.0 when the flow rate of the washing water is 20 BV; preparing sodium carbonate, sodium hydroxide and ammonia water with the concentration of 0.5mol/L as rhenium analytical agents, adding the sodium carbonate, the sodium hydroxide and the ammonia water into a washed resin adsorption column, controlling the flow rate of tail liquid to be 1.5BV, and analyzing the tail liquid by 3.5BV in total, wherein the first 1.5BV sample returns to waste acid for reabsorption, and the rhenium content in the analytical liquid reaches 1440mg/L, which is enriched by 450 times compared with the rhenium content before adsorption; and (3) washing and resolving the resin after resolving rhenium by using a mixed solution of 2% sulfuric acid and 0.2% hydrochloric acid until the pH of tail liquid is about 8, adding 0.8mol/L sodium thiocyanate and 20% sulfuric acid resolving liquid, flowing through an adsorption column from top to bottom, controlling the flow rate of the tail liquid to be 2BV, resolving for 3.5BV totally, returning the first 1BV to the solution before adsorption, wherein the mercury content in the resolving liquid is 2888ppm, and the resolving liquid is 380 times enriched compared with the former solution.
Example 3
Step one, pretreatment of resin
Measuring 40ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, adding 100ml of softened water, statically soaking at normal temperature for swelling for 30h, pouring the softened water after swelling is finished, removing the swollen water, washing the resin with the softened water until the pH value is 7, adding 60ml of 8% ammonia water for alkaline transformation for 10h, washing the resin with the softened water after transformation is finished until the pH value is 8.5, carrying out acid transformation for 30h by using 3.0% mixed acid of sulfuric acid and hydrochloric acid (the mass ratio of the sulfuric acid to the hydrochloric acid is 9:1), and washing the resin with the softened water after transformation is finished until the pH value is 4 for standby.
Step two, pretreatment of the multielement mixed waste acid
Taking SO of certain copper smelting plant in southwest225L of second-stage dynamic wave cooling and purifying waste acid, adding amphoteric polyacrylamide flocculant in ten-thousandth, settling for 2h, and vacuum filtering the multi-element mixed waste acid by using special replacement filter paper for commercially available gold cyanide pregnant solution, wherein the solid content of the filtered multi-element mixed waste acid is 18ppm, and the main components of the multi-element mixed waste acid are shown in the table below.
Element(s) Cu* Pb Se Cd As* F Cl Re Hg H2SO4*
Content (wt.) 5.64 —— 132 77 5.22 2503 1726 17.88 0.90 11.89
Note: unit is g/L
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
The method comprises the steps of loading 40ml of pretreated resin into a transparent glass standard-opening adsorption column with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption column, slowly adding waste acid into the liquid separator, controlling the effluent liquid of the adsorption column to be 10ml/min by adjusting a valve at the lower part of the adsorption column, wherein the adsorption rate is about 15BV, sampling and detecting rhenium and mercury in 400ml of effluent tail liquid, adsorbing 25L multielement mixed waste acid in total, reducing the rhenium and mercury contents of the adsorption tail liquid to 0.19ppm and 2.1ppb respectively after adsorption, and enabling the adsorption rate of rhenium to be greater than 99.44% and the adsorption rate of mercury to be greater than 99.77%.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 40ml resin which is basically saturated in adsorption by using tap water for one section, controlling the flow rate to be about 10BV, detecting the pH of an effluent liquid in real time, changing the pH of a washing water to be about 2 when the resin is washed to be 6BV into quick second-section washing, and quickly washing the residual polybasic mixed waste acid in the resin to be 3.5 when the flow rate of the washing water is 18 BV; preparing ammonia water with the concentration of 2mol/L as a rhenium analysis agent, adding the ammonia water into a washed resin adsorption column, controlling the flow rate of analysis tail liquid to be 3BV, and analyzing the 3BV in total, wherein the previous 1BV sample returns waste acid for re-adsorption, and the rhenium content in the analysis liquid reaches 5000mg/L which is 278 times enriched compared with that before adsorption; adopting sulfuric acid mass: and (3) washing and resolving the resin after resolving rhenium by using a solution with the mass ratio of 1:1 (the total concentration of sulfuric acid is 2.5%), washing until the pH value of a tail solution is about 8.5, adding 1.0mol/L potassium thiocyanate and 15% sulfuric acid resolving solution, flowing through an adsorption column from top to bottom, controlling the flow rate of the tail solution to be 2.5BV, resolving for 2BV totally, returning the first 1BV to a solution before adsorption, wherein the mercury content in the resolving solution is 550ppm, and the mercury content is 611 times that in the resolving solution compared with the former solution.
Example 4
Step one, pretreatment of resin
160ml of D304 type anion exchange resin is measured and poured into a 400ml beaker, 300ml of circulating water is added to statically soak and swell for 16h at normal temperature, after swelling is finished, swelling water is poured out, the resin is washed by the circulating water until the pH value is 7, 200ml of KOH solution with 20 percent is added to carry out immersion and transformation for 30h, after transformation is finished, the resin is washed by the circulating water until the pH value is 9.0, mixed acid of 3.0 percent of sulfuric acid and hydrochloric acid (the mass ratio of the sulfuric acid to the hydrochloric acid is 9:1) is used for carrying out acid immersion and transformation for 5h, and after transformation is finished, the circulating water is washed until the pH value is 2 for standby application.
Step two, pretreatment of the multielement mixed waste acid
Taking SO of a certain copper smelting plant in south China225L of waste acid is purified by secondary dynamic wave cooling, an amphoteric polyacrylamide flocculant is added according to five per million and then settled for 1.8h, the multi-component mixed waste acid is filtered in vacuum by using special replacement filter paper for commercially available gold cyanide pregnant solution, the solid content of the filtered multi-component mixed waste acid is 45ppm, and the main components are shown in the following table.
Element(s) Cu* Pb Se Cd As* F Cl Re Hg H2SO4*
Content (wt.) 1.28 8.23 112 138 8.98 1750 4328 44.30 1.32 7.92
Note: unit is g/L
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Loading pretreated 160ml resin into a transparent glass standard port adsorption column with the diameter of 40mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption column, slowly adding waste acid into the liquid separator, controlling the effluent liquid of the adsorption column to be 32ml/min by adjusting a valve at the lower part of the adsorption column, wherein the adsorption rate is about 12BV, sampling and detecting rhenium and mercury in each 800ml effluent tail liquid, adsorbing 25L multielement mixed waste acid in total, respectively reducing the rhenium and mercury contents of the adsorption tail liquid to 0.15ppm and 3.2ppb after adsorption, and enabling the adsorption rate of rhenium to be greater than 99.66% and the adsorption rate of mercury to be greater than 99.76%;
step four, resolving rhenium and mercury rich in resin
Firstly, washing 80ml of resin which is basically saturated in adsorption by softened water for the first time, controlling the flow rate to be about 4BV, detecting the pH of effluent in real time, changing the pH of washing water to be about 2 when the resin is washed to 7BV into quick second-stage washing, and quickly washing the residual polybasic mixed waste acid in the resin to be 3.2 when the flow rate of the washing water is 25 BV; preparing sodium carbonate and NaOH analytic agents with the concentration of 0.1mol/L, controlling the flow rate of analytic tail liquid to be 3.5BV, and analyzing 6BV in total, wherein the former 2BV sample returns to waste acid for re-adsorption, and the rhenium content in the analytic liquid reaches 3449mg/L, which is 78 times enriched compared with that before adsorption; and (3) washing the resin after resolving rhenium by using tap water until the pH of tail liquid is about 9, adding 1.5mol/L potassium thiocyanate and potassium iodide (molar ratio is 1:1) and 12% sulfuric acid resolving liquid, flowing through an adsorption column from top to bottom, controlling the flow rate of the tail liquid to be 3.0BV, resolving for 3BV totally, returning the first 1BV to the solution before adsorption, wherein the mercury content in the resolving liquid is 198ppm, and enriching the solution by 150 times compared with the front solution.
Example 5
Step one, pretreatment of resin
Removing 75 bags of 25L D304 type anion exchange resin, adding 25 bags of 3 series adsorption columns with the diameter of 0.5m and the net height of 1.5m into each adsorption column, respectively, pumping tap water into the adsorption columns until the liquid level completely passes through the resin liquid level, statically soaking and swelling at normal temperature for 24h, pumping new tap water until the tail liquid pH of the three-stage adsorption columns is about 7 after swelling is finished, pumping 5% NaOH solution until the tail liquid does not pass through the three-stage resin liquid level for alkaline leaching and transformation for 24h, pumping tap water to wash the resin until the pH is 8 after transformation is finished, pumping 5.0% hydrochloric acid solution and then passes through the three adsorption column resin liquid levels, statically performing acid leaching and transformation for 10h, and circularly washing the resin until the pH is 3 after transformation is finished for standby;
step two, pretreatment of the multielement mixed waste acid
SO of copper smelting plant in south China2Two-stage dynamic wave cooling and purifying 35m32 waste acid tanks are arranged in total, amphoteric polyacrylamide flocculant is added into the first waste acid tank according to two parts per million, the retention time of waste acid in the tank is about 3 hours, and then the waste acid passes through 150m2The plate filter press (adopting non-woven filter cloth) filters acid mud, and the filtered liquid is transferred into an intermediate storage tank for 10m3Pumping into a bag type precision filter from an intermediate storage tank for precision filtration, and storing the filtrate into a volume of 35m3The solid content of the waste acid tank was 32ppm, and the main components thereof are shown in Table 5.
Element(s) Cu* Pb Se Cd As* F Cl Re Hg H2SO4*
Content (wt.) 3.21 9.10 —— 252 12.30 1200 5322 29.81 3.00 5.43
Note: unit is g/L
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Pumping pretreated polybasic mixed waste acid into a first adsorption column with diameter of 0.5m × 1.5m from top to bottom, and controlling waste acid flow to be 1.5m by regulating outlet valve of acid-proof pump3And h, enabling the primary adsorption tail liquid to pass through a second adsorption column from top to bottom, enabling the secondary adsorption tail liquid to pass through a third adsorption column from top to bottom, sampling the tertiary adsorption tail liquid every 30min to detect rhenium and mercury, and adsorbing 30m in total3The contents of rhenium and mercury in the three-level tail liquid after adsorption of the multi-element mixed waste acid are respectively reduced to 0.12ppm and 4.8ppb, and the adsorption rates of rhenium and mercury respectively reach 99.60 percent and 99.84 percent.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing the resin in a section of adsorption column which is basically saturated in adsorption by using circulating water for one section, enabling tail liquid to flow out from the bottom of the section of adsorption column and not to flow into the section of adsorption column for two sections, controlling the washing flow rate to be about 5BV, changing the washing flow rate to be 25BV for quick washing when the pH value of tail liquid of one section of washing water is about 2, and washing until the pH value of tail liquid is about 3.5; preparing a NaOH analysis agent with the concentration of 1mol/L, enabling the NaOH analysis agent to flow out of the washed adsorption column from top to bottom through a pump, controlling the flow rate of analysis tail liquid to be 2.5BV, analyzing 4BV in total, wherein the former 1BV sample is returned to waste acid for re-adsorption, and the rhenium content in the analysis liquid reaches 1442mg/L, which is enriched by 48 times compared with that before adsorption; and (2) directly pumping the resin after resolving rhenium into the multi-element mixed waste acid, removing tail liquid from the lower end of the first adsorption column, washing until the pH of the tail liquid is about 6, adding 0.2mol/L potassium thiocyanate and 10% sulfuric acid resolving liquid, flowing through the adsorption column from top to bottom, controlling the flow rate of the tail liquid to be 5.0BV, resolving for 4.5BV totally, returning the first 2BV to the solution before adsorption, wherein the mercury content in the resolving liquid is 457ppm, and enriching for 152 times compared with the former solution.
Example 6
Step one, pretreatment of resin
Measuring 40ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, adding 100ml of softened water, statically soaking at normal temperature for swelling for 30h, pouring the softened water after swelling is finished, removing the swollen water, washing the resin with the softened water until the pH value is 7, adding 60ml of 10% ammonia water for alkaline transformation for 10h, washing the resin with the softened water after transformation is finished until the pH value is 8.5, carrying out acid transformation for 2h by using 2.0% of mixed acid of sulfuric acid and hydrochloric acid (the mass ratio of the sulfuric acid to the hydrochloric acid is 9:1), and washing the resin with the softened water after transformation is finished until the pH value is 4 for standby.
Step two, pretreatment of the multielement mixed waste acid
Taking SO of certain copper smelting plant in southwest2Cooling and purifying 25L of waste acid by secondary dynamic wave, adding amphoteric polyacrylamide flocculant in ten-thousandth, settling for 2h, vacuum filtering the waste acid by using special replacement filter paper for commercial gold cyanide pregnant solution, and filteringThe solid content of the post-polybasic mixed waste acid is 18 ppm.
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
The method comprises the steps of loading 40ml of pretreated resin into a transparent glass standard-opening adsorption column with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption column, slowly adding waste acid into the liquid separator, controlling the effluent liquid of the adsorption column to be 10ml/min by adjusting a valve at the lower part of the adsorption column, wherein the adsorption rate is about 50BV, sampling and detecting rhenium and mercury in each 400ml of effluent tail liquid, adsorbing 25L multielement mixed waste acid in total, and adsorbing the rhenium and mercury contents in the tail liquid to be respectively less than 0.5ppm and 10ppb after adsorption.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 40ml resin which is basically saturated in adsorption by using tap water for one section, controlling the flow rate to be about 2BV, detecting the pH of an effluent liquid in real time, changing the pH of a washing water to be about 2 when the resin is washed to 8BV into quick two-section washing, and quickly washing the residual polybasic mixed waste acid in the resin to be 4.5 when the flow rate of the washing water is 10 BV; preparing ammonia water with the concentration of 2mol/L as a rhenium analysis agent, adding the ammonia water into a washed resin adsorption column, controlling the flow rate of analysis tail liquid to be 5BV, analyzing 2BV in total, wherein the first 1BV sample returns waste acid for re-adsorption, and detecting the content of rhenium in the analysis liquid; adopting sulfuric acid mass: and (3) washing and resolving the resin after resolving rhenium by using a solution with the mass ratio of 1:1 (the total concentration of sulfuric acid is 2.5%), washing until the pH value of a tail solution is about 8.5, adding 1.0mol/L potassium thiocyanate and 15% sulfuric acid resolving solution, flowing through an adsorption column from top to bottom, controlling the flow rate of the tail solution to be 0.5BV, resolving for 8BV totally, returning the first 3BV to a solution before adsorption, and detecting the content of mercury in the resolving solution.
Example 7
Step one, pretreatment of resin
Weighing 50ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, respectively adding 50ml of tap water and 50ml of softened water, statically soaking and swelling for 10 hours at normal temperature, pouring out swelling water after swelling is finished, washing the resin with tap water until the pH value is 7, adding 100ml of 0.1% NaOH, carrying out alkaline leaching and transformation for 5 hours, washing the resin with tap water until the pH value is 9.0 after transformation is finished, carrying out acid leaching and transformation for 8 hours by using 20% of mixed acid of sulfuric acid and hydrofluoric acid (the mass ratio of the sulfuric acid to the hydrofluoric acid is 9:1), and washing the resin with tap water until the pH value is 5 for standby application after transformation is finished.
Step two, pretreatment of the multielement mixed waste acid
Taking SO of copper smelting plant in Huazhong2And (3) cooling and purifying the waste acid by using secondary dynamic waves for 50L, adding an amphoteric polyacrylamide flocculant according to eighty-ten-thousandth of the waste acid, settling for 1.5h, and filtering the multi-element mixed waste acid in vacuum by using special replacement filter paper for commercially available gold cyanide pregnant solution, wherein the solid content of the filtered multi-element mixed waste acid is 17 ppm.
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Loading pretreated 50ml resin into a transparent glass standard port adsorption column with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption column, slowly adding waste acid into the liquid separator, controlling the effluent liquid of the adsorption column to be 21ml/min by adjusting a valve at the lower part of the adsorption column, wherein the adsorption rate is about 25BV, sampling and detecting rhenium and mercury in each 500ml effluent tail liquid, adsorbing 50L multielement mixed waste acid in total, and adsorbing the rhenium and mercury contents in the tail liquid to be respectively less than 0.5ppm and 10ppb after adsorption.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 50ml of resin which is basically saturated in adsorption by using tap water for one section, controlling the flow rate to be about 8BV, detecting the pH of an effluent liquid in real time, changing the pH of a washing water to be about 2 when the resin is washed to be 8BV into quick two-section washing, and quickly washing the residual polybasic mixed waste acid in the resin to be 3.0 when the flow rate of the washing water is 30 BV; preparing sodium carbonate, sodium hydroxide and ammonia water with the concentration of 0.5mol/L as rhenium analytical agents, adding the rhenium analytical agents into a washed resin adsorption column, controlling the flow rate of tail liquid to be 0.5BV, totally analyzing 8BV, returning a first 2BV sample to waste acid for reabsorption, and detecting the content of rhenium in analytical liquid; and (3) washing and resolving the resin after resolving rhenium by using a mixed solution of 2% sulfuric acid and 0.2% hydrochloric acid until the pH of tail liquid is about 8, adding 0.1mol/L sodium thiocyanate and 20% sulfuric acid resolving liquid, flowing through an adsorption column from top to bottom, controlling the flow rate of the tail liquid to be 5BV, resolving for 15BV totally, returning the first 4BV to the solution before adsorption, and detecting the content of mercury in the resolving liquid.
Example 8
Step one, pretreatment of resin
Measuring 80ml of D304 type anion exchange resin, pouring the D304 type anion exchange resin into a 200ml beaker, respectively adding 80ml of circulating water and 80ml of tap water of a copper smelting enterprise, statically soaking and swelling for 15 hours at normal temperature, pouring the mixture after swelling, removing swelling water, washing the mixture with the circulating water and the tap water in a volume ratio of 1:1 until the pH value is 7, adding 200ml of mixed alkali of KOH and ammonia water, wherein the mass concentration of the KOH is 0.2 percent, the concentration of the ammonia water is 0.1 percent, carrying out alkali leaching and transformation for 2 hours, washing the resin with the circulating water until the pH value is 7.5 after transformation is finished, carrying out acid leaching and transformation for 24 hours by using certain multicomponent mixed waste acid for copper smelting in northwest, and not washing the resin again after transformation is finished, and directly using the resin.
Step two, pretreatment of the multielement mixed waste acid
Smelting SO from northwest certain copper2And (3) cooling and purifying 10L of waste acid by using secondary dynamic waves, adding an amphoteric polyacrylamide flocculant by ten-thousandth, settling for 1h, and filtering the multi-element mixed waste acid in vacuum by using special replacement filter paper for commercially available gold cyanide pregnant solution, wherein the solid content of the filtered multi-element mixed waste acid is 20 ppm.
Step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
The method comprises the steps of averagely dividing pretreated 80ml of resin into 2 parts, respectively loading the 2 parts into transparent glass standard-opening adsorption columns with the diameter of 25mm multiplied by 300mm, installing a 500ml spherical liquid separator above the adsorption columns, slowly adding waste acid into the liquid separator, controlling the effluent of the adsorption columns to be 3.33ml/min by adjusting valves at the lower parts of the adsorption columns, controlling the adsorption rate to be about 5BV, adding the effluent tail liquid into another adsorption column filled with 40ml of resin according to the steps, controlling the adsorption speed to be about 5BV, controlling the two adsorption columns to be synchronously performed, sampling and detecting rhenium and mercury for 500ml of the secondary adsorption tail liquid, adsorbing 5L multielement mixed waste acid in total, and respectively reducing the rhenium and mercury contents of the adsorption tail liquid to be less than 0.5ppm and 10ppb after adsorption.
Step four, resolving rhenium and mercury rich in resin
Firstly, washing 40ml of resin which is basically saturated in primary adsorption by softened water for one section, controlling the flow rate to be about 5BV, detecting the pH of effluent in real time, changing the pH of washing water to be about 2 when the resin is washed to 8BV into quick second-section washing, and quickly washing residual polybasic mixed waste acid in the resin to be pH 7 when the flow rate of the washing water is 15 BV; preparing 2.5mol/L sodium carbonate solution as a rhenium analysis agent, adding the solution into a washed resin adsorption column, controlling the flow rate of tail liquid to be 2BV, analyzing 20BV in total, returning the previous 4BV sample to waste acid for re-adsorption, and detecting the content of rhenium in the analysis liquid; and (2) because the mercury content in the waste acid is low, temporarily unresolved mercury is directly returned to the third step for re-adsorption, the resin after resolving rhenium is directly used as the last-stage adsorption no-load resin of the next cycle, rhenium and mercury secondary synergistic co-adsorption is carried out, the mercury content of the secondary tail liquid is less than 10ppb when 4.9L of multi-element mixed waste acid is adsorbed, the adsorbed resin does not resolve rhenium, 0.5mol/L potassium iodide and 20% sulfuric acid base liquid are adopted to directly resolve mercury, an resolving agent slowly passes through saturated resin from top to bottom, the flow rate is 1BV, 3BV is resolved in a co-resolving mode, the former 1BV is returned to the solution before adsorption, and the mercury content in the resolving solution is detected.

Claims (10)

1. A method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-component mixed waste acid is characterized in that the method takes weak alkaline chelating anion exchange resin as an adsorbent to adsorb and treat the copper smelting multi-component mixed waste acid to recover the rhenium and the mercury, and specifically comprises the following steps:
step one, pretreatment of resin
Firstly, soaking macroporous weakly-alkaline chelating anion exchange resin in water to perform swelling treatment, and then sequentially performing washing, alkaline soaking conversion, washing and acid soaking conversion treatment;
step two, pretreatment of the multielement mixed waste acid
Adding a flocculating agent into the to-be-treated multi-element mixed waste acid for flocculation and sedimentation treatment, and then filtering to obtain qualified multi-element mixed waste acid;
step three, synergistic co-adsorption of rhenium and mercury in multi-element mixed waste acid
Enabling the pretreated polybasic mixed waste acid to pass through an adsorption column from top to bottom, and adsorbing rhenium and mercury in the polybasic mixed waste acid by using the anion exchange resin obtained in the step one in the adsorption column;
step four, resolving rhenium and mercury rich in resin
And respectively adopting a rhenium analysis agent and a mercury analysis agent to carry out analysis treatment on the resin after adsorption treatment to obtain a rhenium-containing analysis liquid and a mercury-containing analysis liquid, namely realizing efficient recovery of rhenium and mercury in the copper smelting multi-element mixed waste acid.
2. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in copper smelting according to claim 1, characterized in that: the macroporous weakly basic chelating anion exchange resin is D304 type resin.
3. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting polybasic mixed waste acid according to claim 2, which is characterized in that: the water for the water immersion swelling treatment in the first step is tap water, softened water or circulating water of copper smelting enterprises, and the treatment time is 10-30 hours, preferably 24 hours; the alkali used in alkaline leaching transformation is NaOH, KOH or NH4One or more than one of OH, the mass concentration of the OH is 0.1-20%, preferably 5-10%, the pH of the solution after alkaline leaching transformation is 12-14, and the time of alkaline leaching transformation treatment is 2-30h, preferably 24 h.
4. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in copper smelting according to claim 3, characterized in that: in the step one, the acid used for acid leaching transformation is single acid, multiple mixed acid or multiple mixed waste acid for copper smelting is prepared, the pH value is less than 1, the mass concentration of the acid is 2-20%, preferably 2-5%, and the acid leaching transformation treatment time is 2-30h, preferably 24 h.
5. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in the copper smelting process according to any one of claims 1 to 4, wherein the method comprises the following steps: and in the second step, a polyacrylamide product is adopted as the flocculant, preferably a zwitterionic carboxyl polyacrylamide flocculant, and the addition amount of the flocculant is one ten-thousandth to ten-thousandth of the waste acid to be treated.
6. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in the copper smelting process according to any one of claims 1 to 4, wherein the method comprises the following steps: and in the third step, a multi-stage adsorption column is adopted to sequentially adsorb the multi-element mixed waste acid, and the adsorbed saturated resin is subjected to desorption treatment.
7. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the copper smelting polybasic mixed waste acid according to claim 6, which is characterized in that: the saturation degree of the first-stage adsorption resin in the third step is 30-80%, and the preferred saturation degree of the resin is 60%; enabling the pretreated multi-element mixed waste acid to pass through a first adsorption column from top to bottom, enabling the primary adsorption tail liquid to pass through a second adsorption column, enabling the rhenium or mercury content in the secondary adsorption tail liquid to exceed a preset value, enabling the first adsorption column to be basically saturated, breaking the first adsorption column for resolution, and completing the cyclic utilization of primary resin; changing the last second adsorption column into a first adsorption column of a second cycle, wherein the second adsorption column adopts an adsorption column newly loaded with resin, the adsorption procedure of the multi-element mixed waste acid is that the tail liquid of the first adsorption enters the first adsorption column of the second cycle from top to bottom, and the tail liquid of the second adsorption passes through the second adsorption column from top to bottom, and the cycle is carried out until the content of rhenium or mercury in the tail liquid of the adsorption is lower than a preset value; and after the adsorption is finished, the content of rhenium in the adsorption tail liquid is less than 0.5ppm, the content of mercury is less than 0.01ppm, and tail liquid outlets of all stages of adsorption tail liquid are provided with sampling ports.
8. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in the copper smelting process according to claim 7, wherein the method comprises the following steps: in the fourth step, the resin after adsorption treatment is washed by tap water, softened water or circulating water of copper smelting enterprises, and tap water is preferably selected; when the pH value of the effluent is less than 2, the washing speed is set to be 2-10BV, preferably 4-8 BV; when the pH value of the washing water tail liquid is 2, the flow rate of the washing water is increased to 10-30BV, preferably 15-20 BV; washing the fabric when the pH value of the effluent of the washing water is 3-7, and preferably, the pH value of the effluent of the washing water is 4.5.
9. A process of forming a copper alloy according to claim 8The method for efficiently and selectively adsorbing and recovering rhenium and mercury in the smelting of the multi-element mixed waste acid is characterized by comprising the following steps of: in the fourth step, rhenium absorbed in the resin is analyzed by adopting a non-soft-base rhenium analytical agent which is NaOH or Na2CO3、NaHCO3、NH4One or more OH groups with pH higher than 10 and hydroxyl concentration lower than 5mol/L, preferably 1 mol/L.
10. The method for efficiently and selectively adsorbing and recovering rhenium and mercury from the multi-element mixed waste acid in the copper smelting process according to claim 9, wherein the method comprises the following steps: in the fourth step, the mercury adsorbed in the acidic mercury resolving agent resolving resin containing soft alkali is adopted, the mercury resolving agent is soft alkali salt or acid containing S, and preferably I-、SCN-The concentration of the soluble salt of (4) is 0.1 to 1.5mol/L, preferably 0.5 to 1.0 mol/L.
CN201911317637.2A 2019-12-19 2019-12-19 Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid Active CN110846510B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911317637.2A CN110846510B (en) 2019-12-19 2019-12-19 Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911317637.2A CN110846510B (en) 2019-12-19 2019-12-19 Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid

Publications (2)

Publication Number Publication Date
CN110846510A true CN110846510A (en) 2020-02-28
CN110846510B CN110846510B (en) 2021-08-10

Family

ID=69609936

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911317637.2A Active CN110846510B (en) 2019-12-19 2019-12-19 Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid

Country Status (1)

Country Link
CN (1) CN110846510B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413288A (en) * 2020-03-31 2020-07-14 安徽工业大学 Accurate detection method for rhenium in copper smelting multi-element mixed waste acid
CN115652114A (en) * 2022-12-28 2023-01-31 长沙华时捷环保科技发展股份有限公司 Recycling process of thallium in thallium-containing solution

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1310459A1 (en) * 2001-11-09 2003-05-14 H.C. Starck GmbH & Co. KG Process for recovering Rhenium
CN105384195A (en) * 2015-12-11 2016-03-09 中国地质科学院郑州矿产综合利用研究所 Method for recovering rhenium from molybdenum smelting waste acid
CN109811130A (en) * 2019-02-18 2019-05-28 广州大学 A method of thallium and mercury are recycled from acid waste water is smelted

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1310459A1 (en) * 2001-11-09 2003-05-14 H.C. Starck GmbH & Co. KG Process for recovering Rhenium
CN105384195A (en) * 2015-12-11 2016-03-09 中国地质科学院郑州矿产综合利用研究所 Method for recovering rhenium from molybdenum smelting waste acid
CN109811130A (en) * 2019-02-18 2019-05-28 广州大学 A method of thallium and mercury are recycled from acid waste water is smelted

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111413288A (en) * 2020-03-31 2020-07-14 安徽工业大学 Accurate detection method for rhenium in copper smelting multi-element mixed waste acid
CN111413288B (en) * 2020-03-31 2023-06-30 安徽工业大学 Accurate detection method for rhenium in copper smelting multielement mixed waste acid
CN115652114A (en) * 2022-12-28 2023-01-31 长沙华时捷环保科技发展股份有限公司 Recycling process of thallium in thallium-containing solution

Also Published As

Publication number Publication date
CN110846510B (en) 2021-08-10

Similar Documents

Publication Publication Date Title
US10662075B2 (en) Method and apparatus for the recovery and deep treatment of polluted acid
CN108002580B (en) Method for treating acidic flue gas washing wastewater and application thereof
CN105384195B (en) Method for recovering rhenium from molybdenum smelting waste acid
CN110846510B (en) Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid
CN106947864B (en) A kind of system and its processing method recycling heavy metal from discarded SCR catalyst
CN104862485A (en) Vanadium and tungsten separating and purifying method for spent vanadium and tungsten SCR (selective catalytic reduction) catalysts
CN105238933B (en) It is a kind of from the method containing removing and reclaiming element mercury in sulfur dioxide flue gas
CN107058757A (en) A kind of production method of the separation of Silver from silver-containing liquid waste
CN107519948B (en) Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate
CN109811128B (en) Method for recovering thallium from smelting acidic wastewater and preparing thallium iodide
CN113754162A (en) Method and system for recovering chloride by crystallizing acidic washing wastewater
CN109437444B (en) Recycling treatment device and method for vanadium precipitation mother liquor and washing water
CN102910760A (en) Treatment process of contaminated acid containing heavy metals
CN107354300B (en) A method of the enriching rhenium from Copper making spent acid
CN111392778B (en) Method for deeply purifying and removing potassium from ammonium perrhenate solution
CN109650437B (en) Method for preparing thallium nitrate and thallium sulfate by thallium-containing acidic wastewater
CN107381705B (en) Method for separating and recovering multiple cationic heavy metals in water through phase change regulation
CN107473319B (en) Method for recovering cationic heavy metals in water through phase change regulation
CN102247742A (en) Purification process for sintering flue gas desulfurization solution
CN114797171A (en) Production device and production process for extracting lithium from brine by efficient adsorption method
CN102942274B (en) Treatment method of saline and alkaline wastewater in copper oxide production process
CN115927852A (en) Method for recovering gold, silver and copper from sulfur concentrate calcine washing waste liquid
WO2023097923A1 (en) Low-cost reducing agent for selective precipitation of noble metal ions
CN109811130B (en) Method for recovering thallium and mercury from smelting acid wastewater
CN104496000B (en) The method of arsenic in water body, antimony is removed and is reclaimed in a kind of copper powder displacement

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant