CN110885108B - Efficient harmless treatment method for mine copper cyanide wastewater - Google Patents
Efficient harmless treatment method for mine copper cyanide wastewater Download PDFInfo
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- CN110885108B CN110885108B CN201911131836.4A CN201911131836A CN110885108B CN 110885108 B CN110885108 B CN 110885108B CN 201911131836 A CN201911131836 A CN 201911131836A CN 110885108 B CN110885108 B CN 110885108B
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002351 wastewater Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 52
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010902 straw Substances 0.000 claims abstract description 26
- 239000000440 bentonite Substances 0.000 claims abstract description 21
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 238000004880 explosion Methods 0.000 claims description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 25
- 150000002910 rare earth metals Chemical class 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003851 corona treatment Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- -1 rare earth lanthanum chloride Chemical class 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ZFXTZKMYLJXJDY-UHFFFAOYSA-N copper;oxalonitrile Chemical compound [Cu].N#CC#N ZFXTZKMYLJXJDY-UHFFFAOYSA-N 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/12—Naturally occurring clays or bleaching earth
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- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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Abstract
The invention discloses a high-efficiency harmless treatment method for mine copper cyanide wastewater, which comprises the following steps: step one, preparing modified straw ash: adding the straw ash into deionized water, performing ultrasonic dispersion for 30-40min at the ultrasonic power of 300-400W, then sequentially adding ferric chloride and aluminum chloride, and continuing stirring for 20-30 min. The modified straw ash adopted by the invention is compounded with the modified bentonite after being treated by raw materials such as ferric chloride, aluminum chloride and the like, and finally, a blending system is established, so that the use of the straw ash has the effect of resource recycling, the environment-friendly concept is met, the bentonite is modified by adopting the modified liquid for pouring, the modified liquid can form a hole structure on the bentonite, the straw ash enters the bentonite, and finally, the hole is sealed by the microsphere emulsion, so that the prepared material has very strong specific adsorption capacity.
Description
Technical Field
The invention relates to the technical field of copper cyanide wastewater treatment, and particularly relates to a high-efficiency harmless treatment method for mine copper cyanide wastewater.
Background
Cyanide gold extraction has been carried out for a hundred years, and no suitable gold leaching solvent can be substituted, so that the cyanide gold extraction process will dominate the gold production field in the next decades. With the rapid development of the gold industry, the simple and easy-to-process gold ore resources are less and less, and the copper-containing refractory gold ore resources become one of the main raw materials for gold production. However, when the copper-containing gold ore is treated by a cyanidation gold extraction process, a large amount of low-concentration copper-cyanogen-containing wastewater with total copper and total cyanogen concentration of 70-150 mg/L is generated, and if the wastewater is not treated properly or is not treated and directly discharged, the wastewater will pollute the environment, particularly water resources, and cause serious harm to human health, animals and plants and the whole ecological system.
Although the treatment effect can be achieved in the existing copper-cyanogen wastewater treatment, the treatment efficiency is not high, and the treatment effect cannot be effectively achieved, Chinese patent document CN106219807B discloses a comprehensive treatment method of mine low-concentration copper-cyanogen-containing wastewater, and the operation steps and the process parameters are as follows: step one, removing cyanogen and copper in section I: feeding the mine low-concentration copper-cyanogen-containing wastewater into a first-stage reaction tank with mechanical stirring, adding a cyanogen removing agent A containing copper-sulfur compound slag into the first-stage reaction tank to perform first-stage cyanogen and copper removing reaction, wherein the reaction time is 90-180 min, the pH value of the solution is controlled to be 9-10 in the reaction process, a first-stage cyanogen and copper removing slag slurry 1 is obtained after the reaction is finished, and a polyacrylamide flocculating agent is added at a slag slurry outlet of the first-stage reaction tank; step two, solid-liquid separation in section I: the first-stage cyanogen removal after the polyacrylamide flocculant is added and the copper slag slurry 1 automatically flows to a thickener 1 to carry out first-stage concentration sedimentation to obtain first-stage concentration sedimentation underflow and first-stage concentration sedimentation overflow.
Disclosure of Invention
The invention aims to provide a high-efficiency harmless treatment method for mine copper cyanide wastewater, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-efficiency harmless treatment method for mine copper cyanide wastewater comprises the following steps:
step one, preparing modified straw ash: adding straw ash into deionized water, performing ultrasonic dispersion for 30-40min, wherein the ultrasonic power is 400W and 300-;
step two, preparing modified bentonite: calcining bentonite in a calcining furnace at 1200-1500 deg.C for 20-30min, and pouring with modified liquid at a pouring rate of 1L/min, and coolingCooling, reheating and finally Ga+Performing radiation treatment on the ions to finally obtain modified bentonite;
step three, preparing a blending system: adding modified bentonite and modified straw ash into polystyrene microsphere emulsion, then adding polyethylene wax and lignin, stirring for 20min at the rotating speed of 300-plus-one (500 r/min), then adding ferrocene auxiliary agent, and finally continuing stirring for 1-2h at the rotating speed of 1000-plus-one (2000 r/min), after stirring, drying for 1-2h at 60-70 ℃, after drying, placing in a material bin of a steam explosion machine, introducing saturated steam, and carrying out explosion treatment;
step four, preparing an adsorbent: performing corona treatment on the raw material subjected to steam explosion treatment, and standing for 10-20min under the pressure of 20-30Mpa to obtain adsorbent;
step five: copper cyanide wastewater treatment: and adding the adsorbent prepared in the fourth step into the copper cyanide wastewater, stirring at the rotating speed of 100-200r/min for 40-50min, and finishing stirring.
Preferably, the preparation method of the modifying solution comprises the following steps: wollastonite powder is mixed according to the weight ratio of 1: 2, adding the rare earth additive into the silica sol, then adding the rare earth additive into the silica sol, finally adding the sodium dodecyl sulfate into the silica sol, stirring the mixture for 30 to 40 minutes at the rotating speed of 200-300r/min, and obtaining the modified solution after the stirring is finished.
Preferably, the preparation method of the rare earth additive comprises the steps of adding the rare earth lanthanum chloride into a sulfuric acid solution, continuously stirring at the rotating speed of 200r/min for 30-40min, and obtaining the rare earth additive after stirring.
Preferably, the heat treatment in the second step comprises the following specific steps: firstly heating the bentonite to 800 ℃ for heat preservation for 20-30min, then cooling to 500 ℃ at the speed of 5 ℃/min, then continuing to preserve heat for 35-45min, and finally immediately cooling to room temperature.
Preferably, the Ga is+The irradiation power of the ion for irradiation treatment is 300-500W, the total irradiation time is 20-30min, and specifically, the irradiation is performed for 5min every 2 min.
Preferably, the explosion pressure of the steam explosion treatment in the step three is 2-5 MPa.
Preferably, the explosion pressure of the steam explosion treatment in the third step is 3.5 MPa.
Preferably, the power of the corona treatment is 5-10Kw, the treatment temperature is 20-50 ℃, and the treatment time is 10-20 min.
Compared with the prior art, the invention has the following beneficial effects:
the modified straw ash adopted by the invention is compounded with the modified bentonite after being treated by raw materials such as ferric chloride, aluminum chloride and the like, and finally, a blending system is established, so that the use of the straw ash has the effect of resource recycling, and the environment-friendly concept is met, the bentonite is modified by adopting the modified liquid for pouring, and the modified liquid can form a hole structure on the bentonite, so that the straw ash enters the bentonite, and finally, the hole is sealed by the microsphere emulsion, so that the prepared material has very strong specific adsorption capacity; as is apparent from examples 1 to 3 and comparative examples 1 to 3, the copper recovery rate in example 3 of the present invention was 95.2%, the copper recovery rate in comparative example 3 was 71.3%, example 3 was improved by 13.9% relative to comparative example 3, the total cyanogen content in the outer drain in example 3 was 0.091mg/L, and in comparative example 3 was 0.35mg/L, and it was found that the present invention has a significant recovery effect on copper; meanwhile, the harmless treatment effect can be achieved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the efficient harmless treatment method for mine copper cyanide wastewater comprises the following steps:
step one, preparing modified straw ash: adding straw ash into deionized water, performing ultrasonic dispersion for 30min, wherein the ultrasonic power is 300W, then sequentially adding ferric chloride and aluminum chloride, continuously stirring for 20min at the stirring speed of 500r/min, then adding phosphoric acid, adjusting the pH value to 5.0, then standing for 20-30min, finishing standing, centrifuging, drying, then boiling for 1h with a silane coupling agent KH560, finishing boiling, then adding aluminum silicate, continuously adjusting the pH value to 4.5, and then filtering, washing and drying to obtain modified straw ash;
step two, preparing modified bentonite: calcining bentonite in a calcining furnace at 1200 deg.C for 20min, pouring with modified liquid at a pouring rate of 1L/min, cooling, heat treating, and processing with Ga+Performing radiation treatment on the ions to finally obtain modified bentonite;
step three, preparing a blending system: adding modified bentonite and modified straw ash into polystyrene microsphere emulsion, then adding polyethylene wax and lignin, firstly stirring at the rotating speed of 300r/min for 20min, then adding a ferrocene auxiliary agent, finally continuing stirring at the rotating speed of 1000r/min for 1h, finishing stirring, drying at 60 ℃ for 1h, finishing drying, placing in a material bin of a steam explosion machine, introducing saturated steam, and carrying out explosion treatment;
step four, preparing an adsorbent: performing corona treatment on the raw material subjected to the steam explosion treatment, and standing for 10min under the pressure of 20Mpa to obtain the adsorbent;
step five: copper cyanide wastewater treatment: and D, adding the adsorbent prepared in the step four into the copper cyanide wastewater, stirring at the rotating speed of 100r/min for 40min, and finishing stirring.
The preparation method of the modified solution in this example is as follows: wollastonite powder is mixed according to the weight ratio of 1: 2, adding the rare earth additive into the silica sol, then adding the rare earth additive into the silica sol, finally adding the sodium dodecyl sulfate into the silica sol, stirring the mixture for 30min at the rotating speed of 200r/min, and obtaining the modified solution after the stirring.
The preparation method of the rare earth additive of the embodiment includes adding the rare earth lanthanum chloride into a sulfuric acid solution, then continuing stirring for 30min at a rotation speed of 200r/min, and obtaining the rare earth additive after stirring.
The heat treatment in the second step of this embodiment specifically includes the following steps: firstly heating the bentonite to 700 ℃, preserving heat for 20min, then cooling to 500 ℃ at the speed of 5 ℃/min, then continuing preserving heat for 35-45min, and finally immediately cooling to room temperature.
Ga of the example+The irradiation power of the ion for irradiation treatment is 300W, the total irradiation time is 20min, and the irradiation is performed for 5min every 2 min.
The burst pressure of the steam explosion treatment in the third step of this example was 2 Mpa.
The power of the corona treatment in this example was 5Kw, the treatment temperature was 20 ℃ and the treatment time was 10 min.
Example 2:
the efficient harmless treatment method for mine copper cyanide wastewater comprises the following steps:
step one, preparing modified straw ash: adding straw ash into deionized water, performing ultrasonic dispersion for 40min, wherein the ultrasonic power is 400W, then sequentially adding ferric chloride and aluminum chloride, continuously stirring for 30min at the stirring speed of 1000r/min, then adding phosphoric acid, adjusting the pH value to 6.0, then standing for 30min, finishing standing, centrifuging, drying, then boiling with a silane coupling agent KH560 for 2h, finishing boiling, then adding aluminum silicate, continuously adjusting the pH value to 5.5, and then filtering, washing and drying to obtain modified straw ash;
step two, preparing modified bentonite: calcining bentonite in a calcining furnace at 1500 deg.C for 30min, pouring with modified liquid at a pouring rate of 1L/min, cooling, heat treating, and processing with Ga+Performing radiation treatment on the ions to finally obtain modified bentonite;
step three, preparing a blending system: adding modified bentonite and modified straw ash into polystyrene microsphere emulsion, then adding polyethylene wax and lignin, firstly stirring at the rotating speed of 500r/min for 20min, then adding ferrocene auxiliary agent, finally continuing stirring at the rotating speed of 2000r/min for 2h, finishing stirring, drying at 70 ℃ for 2h, finishing drying, placing in a material bin of a steam explosion machine, introducing saturated steam, and carrying out explosion treatment;
step four, preparing an adsorbent: performing corona treatment on the raw material subjected to the steam explosion treatment, and standing for 20min under the pressure of 30Mpa to obtain the adsorbent;
step five: copper cyanide wastewater treatment: and D, adding the adsorbent prepared in the fourth step into the copper cyanide wastewater, stirring at the rotating speed of 200r/min for 50min, and finishing stirring.
The preparation method of the modified solution in this example is as follows: wollastonite powder is mixed according to the weight ratio of 1: 2, adding the rare earth additive into the silica sol, then adding the rare earth additive into the silica sol, finally adding the sodium dodecyl sulfate into the silica sol, stirring the mixture at the rotating speed of 300r/min for 40min, and obtaining the modified solution after the stirring.
The preparation method of the rare earth additive of the embodiment includes adding the rare earth lanthanum chloride into a sulfuric acid solution, then continuing to stir at a rotation speed of 200r/min for 40min, and obtaining the rare earth additive after stirring.
The heat treatment in the second step of this embodiment specifically includes the following steps: the bentonite is heated to 800 ℃ and is kept warm for 30min, then the bentonite is cooled to 500 ℃ at the speed of 5 ℃/min, then the heat is kept for 45min, and finally the bentonite is immediately cooled to the room temperature.
Ga of the example+The irradiation power of the ion for irradiation treatment is 500W, the total irradiation time is 30min, and the irradiation is performed for 5min every 2 min.
The burst pressure of the steam explosion treatment in the third step of this example was 5 Mpa.
The power of the corona treatment in this example was 10Kw, the treatment temperature was 50 ℃ and the treatment time was 20 min.
Example 3:
the efficient harmless treatment method for mine copper cyanide wastewater comprises the following steps:
step one, preparing modified straw ash: adding straw ash into deionized water, performing ultrasonic dispersion for 35min, wherein the ultrasonic power is 350W, then sequentially adding ferric chloride and aluminum chloride, continuously stirring for 20-30min at the stirring speed of 500 plus 1000r/min, then adding phosphoric acid, adjusting the pH value to 5.4, then standing for 25min, finishing standing, centrifuging, drying, boiling with a silane coupling agent KH560 for 1-2h, finishing boiling, then adding aluminum silicate, continuously adjusting the pH value to 5.0, and then filtering, washing and drying to obtain modified straw ash;
step two, preparing modified bentonite: calcining bentonite in a calcining furnace for 25min at 1350 deg.C, pouring with modified liquid at a pouring rate of 1L/min, cooling, heat treating, and processing with Ga+Performing radiation treatment on the ions to finally obtain modified bentonite;
step three, preparing a blending system: adding modified bentonite and modified straw ash into polystyrene microsphere emulsion, then adding polyethylene wax and lignin, firstly stirring at a rotating speed of 400r/min for 20min, then adding a ferrocene auxiliary agent, finally continuously stirring at a rotating speed of 1500r/min for 1-2h, finishing stirring, drying at 65 ℃ for 1.5h, finishing drying, placing in a material bin of a steam explosion machine, introducing saturated steam, and carrying out explosion treatment;
step four, preparing an adsorbent: performing corona treatment on the raw material subjected to the steam explosion treatment, and standing for 15min under the pressure of 25Mpa to obtain the adsorbent;
step five: copper cyanide wastewater treatment: and adding the adsorbent prepared in the fourth step into the copper cyanide wastewater, stirring at the rotating speed of 150r/min for 45min, and finishing stirring.
The preparation method of the modified solution in this example is as follows: wollastonite powder is mixed according to the weight ratio of 1: 2, adding the rare earth additive into the silica sol, then adding the rare earth additive into the silica sol, finally adding the sodium dodecyl sulfate into the silica sol, stirring the mixture for 35min at the rotating speed of 250r/min, and obtaining the modified solution after the stirring.
The preparation method of the rare earth additive of the embodiment includes adding the rare earth lanthanum chloride into a sulfuric acid solution, then continuing stirring for 30-40min at a rotation speed of 200r/min, and obtaining the rare earth additive after stirring.
The heat treatment in the second step of this embodiment specifically includes the following steps: the bentonite is heated to 750 ℃ and is kept warm for 25min, then the bentonite is cooled to 500 ℃ at the speed of 5 ℃/min, then the heat is kept for 40min, and finally the bentonite is immediately cooled to the room temperature.
Ga of the example+The irradiation power of the ion for irradiation treatment is 400W, the total irradiation time is 25min, and the irradiation is performed for 5min every 2 min.
The burst pressure of the steam explosion treatment in the third step of this example was 3.5 MPa.
The power of the corona treatment in this example was 7.5Kw, the treatment temperature was 35 ℃ and the treatment time was 15 min.
Comparative example 1.
The materials and preparation process were substantially the same as those of example 3, except that bentonite was not modified.
Comparative example 2.
The materials and preparation process were essentially the same as those of example 3, except that no lignin was added to the preparation of the blend system.
Comparative example 3.
The materials and preparation process were substantially the same as those of example 3, except that the treatment was carried out using conventional raw materials.
The results of the performance tests of examples 1 to 3 and comparative examples 1 to 3 are as follows
| Copper recovery (%) | Content of total cyanogen in external drainage (mg/L) | |
| Example 1 | 93.5 | 0.12 |
| Example 2 | 94.1 | 0.095 |
| Example 3 | 95.2 | 0.091 |
| Comparative example 1 | 85.3 | 0.21 |
| Comparative example 2 | 87.6 | 0.17 |
| Comparative example 3 | 71.3 | 0.35 |
As is apparent from examples 1 to 3 and comparative examples 1 to 3, the copper recovery rate in example 3 of the present invention was 95.2%, the copper recovery rate in comparative example 3 was 71.3%, example 3 was improved by 23.9% relative to comparative example 3, the total cyanogen content in the outer drain in example 3 was 0.091mg/L, and in comparative example 3 was 0.35mg/L, and it was found that the present invention has a significant recovery effect on copper; meanwhile, the harmless treatment effect can be achieved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A high-efficiency harmless treatment method for mine copper cyanide wastewater is characterized by comprising the following steps:
step one, preparing modified straw ash: adding straw ash into deionized water, performing ultrasonic dispersion for 30-40min, wherein the ultrasonic power is 400W and 300-;
step two, preparing modified bentonite: calcining bentonite in a calcining furnace at 1200-1500 deg.C for 20-30min, pouring with a modifying solution at a pouring rate of 1L/min, cooling, performing heat treatment, and finally performing Ga precipitation+Performing radiation treatment on the ions to finally obtain the modified bentonite, wherein the preparation method of the modified liquid comprises the following steps: wollastonite powder is mixed according to the weight ratio of 1: 2, adding the rare earth auxiliary agent into the silica sol, then adding the rare earth auxiliary agent into the silica sol, finally adding sodium dodecyl sulfate into the silica sol, then stirring the mixture for 30 to 40 minutes at the rotating speed of 200-300r/min, and obtaining a modified solution after the stirring is finished, wherein the preparation method of the rare earth auxiliary agent comprises the steps of adding the rare earth lanthanum chloride into a sulfuric acid solution, then continuously stirring the mixture for 30 to 40 minutes at the rotating speed of 200r/min, and obtaining the rare earth auxiliary agent after the stirring is finished;
step three, preparing a blending system: adding modified bentonite and modified straw ash into polystyrene microsphere emulsion, then adding polyethylene wax and lignin, stirring for 20min at the rotating speed of 300-plus-one (500 r/min), then adding ferrocene auxiliary agent, and finally continuing stirring for 1-2h at the rotating speed of 1000-plus-one (2000 r/min), after stirring, drying for 1-2h at 60-70 ℃, after drying, placing in a material bin of a steam explosion machine, introducing saturated steam, and carrying out explosion treatment;
step four, preparing an adsorbent: performing corona treatment on the raw material subjected to steam explosion treatment, and standing for 10-20min under the pressure of 20-30Mpa to obtain adsorbent;
step five: copper cyanide wastewater treatment: and adding the adsorbent prepared in the fourth step into the copper cyanide wastewater, stirring at the rotating speed of 100-200r/min for 40-50min, and finishing stirring.
2. The efficient harmless treatment method for mine copper cyanide wastewater according to claim 1, characterized in that the heat treatment in the second step comprises the following specific steps: firstly heating the bentonite to 800 ℃ for heat preservation for 20-30min, then cooling to 500 ℃ at the speed of 5 ℃/min, then continuing to preserve heat for 35-45min, and finally immediately cooling to room temperature.
3. The efficient harmless treatment method for mine copper cyanide wastewater according to claim 1, characterized in that the Ga+The irradiation power of the ion for irradiation treatment is 300-500W, the total irradiation time is 20-30min, and specifically, the irradiation is performed for 5min every 2 min.
4. The efficient harmless treatment method for mine copper cyanide wastewater according to claim 1, characterized in that the explosion pressure of the steam explosion treatment in the third step is 2-5 Mpa.
5. The efficient harmless treatment method for mine copper cyanide wastewater according to claim 4, characterized in that the explosion pressure of the steam explosion treatment in the third step is 3.5 MPa.
6. The efficient harmless treatment method for mine copper cyanide wastewater according to claim 1, characterized in that the power of the corona treatment is 5-10kW, the treatment temperature is 20-50 ℃, and the treatment time is 10-20 min.
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