CN109082525A - A method of raising relates to weight dangerous waste bioleaching-regeneration enrichment efficiency - Google Patents
A method of raising relates to weight dangerous waste bioleaching-regeneration enrichment efficiency Download PDFInfo
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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- 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
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- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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Abstract
The present invention relates to a kind of raisings to relate to weight dangerous waste bioleaching-regeneration enrichment efficiency method, belongs to dangerous solid wastes recycling processing technology field.The occurrence status that a variety of roasting techniques are used to relate to the pretreatment of weight dangerous waste to eliminate organic matter, remove fluorine removal chloride ion, change valuable metal, to improve the bioleaching-regeneration enrichment efficiency for relating to weight dangerous waste valuable metal.By selecting the regulation of roasting technique operating parameter and additive, achievable different type relates to the occurrence status variation that the removing of toxic organic compound and fluorine chloride ion and indissoluble gold in weight dangerous waste belong to, electroplating sludge regeneration times are increased to 15 times or more by 8-10 times after roasting pretreatment, pickling sludge is increased to 10 times or more by 1-2 times, useless hydrogenation catalyst organic metal cobalt nickel extracting efficiency is increased to 90%-95% by 70%, and waste and old lithium ion battery solid-to-liquid ratio is increased to 2.5% or more by 1.0%.Therefore, the final enriched concentration for relating to valuable metal in weight dangerous waste is significantly increased, and creates advantageous condition for subsequent metal purification and recovery.
Description
Technical field
The present invention relates to the methods that a kind of pretreatment of low-temperature bake relates to biology extraction valuable metal after weight dangerous waste, belong to danger
Reclamation of solid wastes processing technology field.
Background technique
It relates to weight dangerous waste and refers to the hazardous waste containing toxic metals, be by sources divided into material source dangerous waste and industrial source dangerous waste.
The former includes spent catalyst, old and useless battery, discarded solar panel, electronic waste, abandoned printed circuit board etc.；The latter's packet
Include plating waste residue, acid cleaning waste slag, melting waste slag, flying ash etc..Relating to weight, dangerous waste is many kinds of, enormous amount.New edition " country's danger
Dangerous waste register " 46 major class are shared, it relates to weight dangerous waste and occupies 17 major class.The industrial dangerous waste yield about 60,000,000 in the whole nation in 2016
Ton, relating to weight dangerous waste is more than 20,000,000 tons.Wherein old and useless battery, spent catalyst, discarded photovoltaic panel be at hundreds of thousands of tonnes, and electric
Waste residue, acid cleaning waste slag, melting waste slag are plated then at millions of tonnes.
It relates to weight dangerous waste and usually contains severe toxicity/toxic metals such as chromium, cadmium, lead, arsenic, mercury of high concentration etc., environmental hazard is serious.
The improper disposition for relating to weight dangerous waste is one of the main cause of current China's heavy-metal contaminated soil large area outburst, and occurs again and again in the recent period
Much relate to arsenic, relate to lead, relate to cadmium pollution public hazard incident be then directly derived from relate to weight dangerous waste illegal dumping.On the other hand, it relates to and endangers again
It is useless often to contain valuable/high price/rare precious metal such as Au Ag Pt Pd, rhodium, indium, gallium, germanium, copper, cobalt, nickel, molybdenum, lithium, zinc, manganese etc.,
Sometimes content is even more than raw ore, can be rated as secondary mineral products.Valuable, high price and rare precious metal are recycled from relating in weight dangerous waste, for answering
It is of great significance to the metal shortage of the following global range, represents the developing direction of such dangerous waste processing disposition.
Bioleaching-regeneration beneficiation technologies realize solid phase material under the temperate condition of normal temperature and pressure by microbial action
The efficient leaching of middle metal target, then be catalyzed by solid phase biological and to realize the failure drip circular regeneration of liquid, more batches of solid phase material
The drip liquid enrichment of secondary drip leaching and metal target.Drip liquid regeneration substantially reduces the consumption of culture medium and water；Metal target is enriched with then
Significantly reduce the cost of later separation purifying.It may be implemented to relate to using bioleaching-regeneration beneficiation technologies valuable in weight dangerous waste
The efficient extraction of metal and fast enriching can realize target gold particularly with the lower weight dangerous waste that relates to of content by circular regeneration
The drip liquid of category is concentrated, and shows brilliant application prospect, thus extensive concern and research by domestic and foreign scholars.
It relates to weight dangerous waste and not only contains valuable metal but also poisonous and hazardous substance and ion containing there are many, as electroplating sludge contains
There are surfactant and organic complexing agent, pickling sludge contains the fluorine, chlorine and nitrate ion of high concentration, and dead catalyst contains more
Kind oil component and catabolite, old and useless battery contain considerable organic bond and fluorine class electrolyte etc..In bioleaching-
It regenerates in enrichment process, these harmful substances and ion can be discharged and are enriched among drip liquid and generate toxicity to drip leaching microorganism
Effect causes circular regeneration to interrupt and terminates with metal enrichment.Therefore, from relate to weight dangerous waste in separation remove these toxic organic compounds and
Fluorine chloride ion is of great significance for relating to the practical application of weight dangerous waste bioleaching-regeneration beneficiation technologies.
Roasting is that lower than heating under furnace charge melting temperature oxidation, reduction are occurred for ore or other solid materials
Or other chemical changes are to change the preprocessing process of the phase structure of material, constituent component, form valence state.By calcination atmosphere
It is divided into reduction roasting, oxidizing roasting, receiving roasting, chloridising roasting, sulfating roasting etc. with the difference of conditioning medicament.Wherein, oxygen
Organic matter in solid phase material can be removed by changing roasting, add silicon humidification roasting that can remove fluorine removal chloride ion, and sulfating roasting can be
The sulfide of hardly possible leaching is converted into the sulfate species easily soaked.It therefore, can by the compound of different type roasting technique and optimization
With removal relate to weight dangerous waste in harmful organic matter and fluorine chloride ion and the occurrence status for changing valuable metal, eliminate harmful substance and
The poisonous effect of ion pair drip leaching microorganism improves the circular regeneration efficiency of failure drip liquid, improves the leaching and richness of valuable metal
Collect efficiency, solves to relate to the crucial common problem in weight dangerous waste bioleaching-regeneration enrichment.
Summary of the invention
The present invention weighs the nuisances such as surfactant, organic complex, fluorine chloride ion present in dangerous waste to solve to relate to
Verify the toxic action of drip leaching microorganism and improvement relate to the Bioleaching efficiency of difficult drip leaching metal in weight dangerous waste, by it is easy to operate,
Be easy to regulate and control, suitable for scale disposition roasting technique be used for relate to weight dangerous waste pretreatment with eliminate organic matter, go fluorine and chlorine removal from
Son, the occurrence status for changing valuable metal, so that the bioleaching-regeneration enrichment efficiency for relating to weight dangerous waste valuable metal is improved, this
It is of great significance for relating to valuable metal recovery in weight dangerous waste.
The purpose is realized by following steps:
Step 1 relates to weight dangerous waste for different type, sieve is crushed or ground after drying 6-24 hours at 60-120 DEG C
50-200 microns of partial size of granular material is obtained by filtration；
Granular material and various solid additives are uniformly mixed (silica, sulphur, Asia by step 2 by a certain percentage
Sodium sulphate, sodium thiosulfate, calcium chloride or/and sodium chloride etc., weight ratio 1.0%-10%, 5-20 grams of total weight), in 300-
(100 × 100 × 100mm) roasts 10-60 minutes (depending on different material or anoxic be closed or input air in 1200 DEG C of Muffle furnaces
Or/and it is passed through vapor, 0.25 liter -2.5 liters/min)；By roasting removal organic matter, fluorine chloride ion or change object phase property
Solid material is slowly cooled to room temperature；
Step 3, biological leaching liquor preparation, to culture solution inoculation Thiobacillus thioxidans, Thiobacillus ferrooxidans and thermophilic iron hook
The mixing acidophilus sulphur iron-oxidizing bacteria group (each bacterium inoculum concentration is 2.5%-10%, V/V) for holding the compositions such as spirillum, culture solution includes:
KH2PO4, 0.5-2.0g/L；Na2HPO4, 0.5-2.0g/L；KNO3, 0.5-2.0g/L；(NH4)2SO4, 0.5-2.0g/L；NaCl,
0.5-2.0g/L；MgSO4.7H2O, 0.25-1.0g/L；CaCl2, 0.25-1.0g/L；Na2S2O3, 4.0-24.0g/L；Sulphur or
Sulphur cream or sludge containing sulphur, 4.0-24.0g/L；Pyrite, 4.0-24.0g/L；Solvent is tap water or recycled water or river and lake water,
Natural ph；Culture medium after inoculation is cultivated 6-9 days, shaking speed 60-180rpm in water bath with thermostatic control shaking table, cultivation temperature
25-40℃；Detection architecture pH, ORP, Fe2+, Fe3+Change with cell concentration, is down to 0.8-1.2, Fe to pH2+In 100-400mg/
L,Fe3+In 200-800mg/L, cell concentration rises to 108A/mL or more, is centrifugated thallus and solid energy substrate produces work
Property drip immersion liquid, isolated thallus and energy substrate are then kept in stand-by；
Step 4, roasting pretreatment relate to the biology extraction of weight dangerous waste, will relate to weight dangerous waste (solid-to-liquid ratio after roasting pretreatment
2.5%-10%, W/V) it is added in activity drip immersion liquid, it is placed in water bath with thermostatic control shaking table and extracts 3-12h, shaking speed 60-
180rpm, 25-35 DEG C of temperature；After metal target reaches extraction terminal, centrifuge separation failure drip immersion liquid and leaching residue, failure
Drip liquid is used to recycle extraction again after regeneration；
Step 5, failure drip liquid regeneration and circulation extraction, the thallus of step 3 separation and energy substrate mixture are added
Failure immersion liquid among (energy substrate can suitably add with guarantee react needed for concentration), be placed in water bath with thermostatic control shaking table cultivate with
Realize regeneration；PH in detection architecture, ORP, Fe2+, Fe3+Change with cell concentration, is down to 0.8-1.2, Fe to pH2+In 100-
400mg/L,Fe3+In 200-800mg/L, cell concentration rises to 108A/mL or more is centrifugated thallus and solid energy substrate
Activity drip immersion liquid is produced, isolated thallus and energy substrate are then kept in stand-by；Step three and four is repeated, 10-20 times, realizes roasting
Pretreatment relates to drip liquid regeneration-circulation extraction of weight dangerous waste to realize the accumulation enrichment of valuable metal.
Beneficial effect
By the regulation of roasting technique operating parameter and additive selection, different type may be implemented relate to toxic to have in weight dangerous waste
The occurrence status that the removing of machine object and fluorine chloride ion and indissoluble gold belong to changes, the regeneration times of electroplating sludge after roasting pretreatment
It is increased to 15 times or more by 8-10 times, pickling sludge is increased to 10 times or more by 1-2 times, and give up hydrogenation catalyst organic metal cobalt nickel
Extracting efficiency be increased to 90%-95% by 70%, the solid-to-liquid ratio of waste and old lithium ion battery is increased to 2.5% or more by 1.0%.
Therefore, the final enriched concentration for relating to valuable metal in weight dangerous waste is significantly increased, and creates favorably for subsequent metal purification and recovery
Condition.
Specific embodiment
Case study on implementation 1:
Bioleaching-regeneration that roasting pretreatment improves valuable metal nickel in pickling sludge is enriched with efficiency.
100 microns of partial size of granular material is obtained by filtration in grinding after pickling sludge is dried 12 hours at 105 DEG C.By grain
Diameter is that 100 microns of silica is added among powdery pickling sludge and is uniformly mixed by 5.0% weight ratio.By 10 grams of acid
It washes sludge-silica mixture and is placed in 950 DEG C of Muffle kiln roastings 30 minutes, air and vapor are passed through during roasting, lead to
Enter speed and keeps 0.5 liter/min.Culture solution (Na is extracted to biology2HPO4, 1.0g/L；(NH4)2SO4, 1.0g/L；KNO3,
1.0g/L；NaCl, 1.0g/L；MgSO4.7H2O, 0.5g/L；CaCl2, 0.25g/L；Sulphur, 12.0g/L；Pyrite, 4.0g/L)
The mixing acidophilus sulphur iron-oxidizing bacteria group of middle inoculation Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum composition
(inoculum concentration 10%, V/V) cultivates 10 days (120rpm, 30 DEG C) system pH in water bath with thermostatic control shaking table and is down to 0.8, Fe2+Concentration is
320mg/L, Fe3+Concentration is 700mg/L, and cell concentration reaches 4.0 × 108Under a/mL, 10000r/min be centrifugated thallus and
Energy substrate obtains activity drip immersion liquid, and separating thallus and energy substrate mixture are kept in.Pickling after roasting pretreatment is dirty
Mud (10.0%, W/V) is added among the active leaching liquor of pH 0.8, is placed in extraction 6h (140rpm, 30 DEG C) in water bath with thermostatic control shaking table,
Valuable metal nickel reaches leaching terminal, and dissolving out concentration at that time is 2.1g/L.Be centrifuged (3000r/min, 10min) separation leaching liquor and
Leaching residue.The leaching liquor that will fail is mixed with the thallus and energy substrate separated before, and is cultivated again in water bath with thermostatic control shaking table
It is raw；Roasting pretreatment pickling sludge is added again when pH is down to 0.8, so failure drip liquid regeneration-circulation is soaked after extracting 10 times
Nickel is enriched with to 21g/L in extract.
Case study on implementation 2:
Roasting pretreatment, which improves, adds the bioleaching of molybdenum and cobalt-regeneration in hydrogen dead catalyst to be enriched with efficiency.
100 microns of partial size of granular material is obtained by filtration in grinding after dead catalyst is dried 16 hours at 100 DEG C.It will be sub-
Sodium sulphate is added among powdery dead catalyst and is uniformly mixed by 10.0% weight ratio.By 20 grams of dead catalyst-sulfurous acid
Sodium mixture is placed in 550 DEG C of Muffle kiln roastings 60 minutes, and air is passed through during roasting, is passed through speed and is kept for 2.0 liters/min.
Culture solution (Na is extracted to biology2HPO4, 1.0g/L；(NH4)2SO4, 1.0g/L；KNO3, 1.0g/L；NaCl, 1.0g/L；
MgSO4.7H2O, 0.5g/L；CaCl2, 0.25g/L；Sulphur, 8.0g/L；Pyrite, 8.0g/L) in inoculation Thiobacillus thioxidans,
The mixing acidophilus sulphur iron-oxidizing bacteria group (inoculum concentration 5.0%, V/V) of Thiobacillus ferrooxidans and leptospirillum ferriphilum composition,
12 days (120rpm, 30 DEG C) system pH are cultivated in water bath with thermostatic control shaking table is down to 0.8, Fe2+Concentration is 400mg/L, Fe3+Concentration is
820mg/L, cell concentration reach 4.0 × 108It is centrifugated thallus under a/mL, 10000r/min and energy substrate obtains activity
Immersion liquid is dripped, separating thallus and energy substrate mixture are kept in.Dead catalyst (5.0%, W/V) after roasting pretreatment is added
Among the active leaching liquor of pH 0.8, it is placed in extraction 6h (140rpm, 30 DEG C) in water bath with thermostatic control shaking table, valuable metal molybdenum cobalt reaches leaching
Terminal out, two metal dissolving concentrations are respectively 2.3 and 1.9g/L at that time.It is centrifuged (3000r/min, 10min) separation failure
Leaching liquor and leaching residue.The leaching liquor that will fail is mixed with the thallus and energy substrate separated before, and in water bath with thermostatic control shaking table
Middle culture regeneration；Dead catalyst is added again when pH is down to 0.8, so failure drip liquid regeneration-circulation extracts after extracting 12 times
Molybdenum cobalt is enriched with respectively to 28 and 23g/L in liquid.
Case study on implementation 3:
Roasting pretreatment improves Copper in Electroplating Sludge and bioleaching-regeneration of nickel is enriched with efficiency
100 microns of partial size of granular material is obtained by filtration in grinding after electroplating sludge is dried 12 hours at 105 DEG C.By 20
Gram electroplating sludge is placed in 400 DEG C of Muffle kiln roastings 60 minutes, and air is passed through during roasting, is passed through speed and is kept for 1.0 liters/min
Clock.Culture solution (Na is extracted to biology2HPO4, 1.0g/L；(NH4)2SO4, 1.0g/L；KNO3, 1.0g/L；NaCl, 1.0g/L；
MgSO4.7H2O, 0.5g/L；CaCl2, 0.25g/L；Sulphur, 14.0g/L；Pyrite, 2.0g/L) in inoculation Thiobacillus thioxidans,
The mixing acidophilus sulphur iron-oxidizing bacteria group (inoculum concentration 10.0%, V/V) of Thiobacillus ferrooxidans and leptospirillum ferriphilum composition,
10 days (120rpm, 30 DEG C) system pH are cultivated in water bath with thermostatic control shaking table is down to 0.8, Fe2+Concentration is 250mg/L, Fe3+Concentration is
480mg/L, cell concentration reach 4.0 × 108It is centrifugated thallus under a/mL, 10000r/min and energy substrate obtains activity
Immersion liquid is dripped, separating thallus and energy substrate mixture are kept in.Electroplating sludge (5.0%, W/V) after roasting pretreatment is added
Among the active leaching liquor of pH 0.8, it is placed in extraction 6h (140rpm, 30 DEG C) in water bath with thermostatic control shaking table, valuable metal cupro-nickel reaches leaching
Terminal out, two metal dissolving concentrations are respectively 2.6 and 1.7g/L at that time.It is centrifuged (3000r/min, 10min) separation failure
Leaching liquor and leaching residue.The leaching liquor that will fail is mixed with the thallus and energy substrate separated before, and in water bath with thermostatic control shaking table
Middle culture regeneration；Electroplating sludge is added again when pH is down to 0.8, so failure drip liquid regeneration-circulation extracts after extracting 10 times
Molybdenum cobalt is enriched with respectively to 26 and 17g/L in liquid.
Claims (6)
1. a kind of method that raising relates to weight dangerous waste bioleaching-regeneration enrichment efficiency, main feature the following steps are included:
Step 1 relates to weight dangerous waste for different type, the screen to filtrate is crushed or ground after drying 6-24 hours at 60-120 DEG C
Obtain 50-200 microns of partial size of granular material；
Step 2 uniformly mixes granular material and various solid additives by a certain percentage, in Muffle furnace (100 × 100 ×
It 100mm) roasts 10-60 minutes, maturing temperature is 300-1200 DEG C, by roasting removal organic matter, fluorine chloride ion or changes object phase
The solid material of property is slowly cooled to room temperature；
Step 3, biological leaching liquor preparation, to culture solution inoculation Thiobacillus thioxidans, Thiobacillus ferrooxidans and thermophilic iron hook end spiral shell
The mixing acidophilus sulphur iron-oxidizing bacteria group of the compositions such as bacterium is revolved, solvent is tap water or recycled water or river and lake water, natural ph；After inoculation
Culture medium cultivated in water bath with thermostatic control shaking table 6-9 days, shaking speed 60-180rpm, 25-40 DEG C of cultivation temperature；Detection architecture
PH, ORP, Fe2+, Fe3+Change with cell concentration, is down to 0.8-1.2, Fe to pH2+In 100-400mg/L, Fe3+In 200-
800mg/L, cell concentration rise to 108A/mL or more, is centrifugated thallus and solid energy substrate produces activity drip immersion liquid, point
From thallus and energy substrate then keep in it is stand-by；
Step 4, roasting pretreatment relate to the biology extraction of weight dangerous waste, will relate to weight dangerous waste by mass volume ratio after roasting pretreatment
2.5%-10% is added in activity drip immersion liquid, is placed in water bath with thermostatic control shaking table and extracts 3-12h, shaking speed 60-180rpm, temperature
25-35℃；After metal target reaches extraction terminal, centrifuge separation failure drip immersion liquid and leaching residue, failure drip liquid is through regenerating
Afterwards for circulation extraction again；
Step 5, failure drip liquid regeneration and circulation extraction, are added failure for the thallus of step 3 separation and energy substrate mixture
Among immersion liquid, it is placed in water bath with thermostatic control shaking table and cultivates to realize regeneration；PH in detection architecture, ORP, Fe2+, Fe3+And thallus
Concentration variation, is down to 0.8-1.2, Fe to pH2+In 100-400mg/L, Fe3+In 200-800mg/L, cell concentration rises to 108A/
ML or more is centrifugated thallus and solid energy substrate and produces activity drip immersion liquid, isolated thallus and energy substrate then keep in
With；It repeats step three and four 10-20 times, drip liquid regeneration-circulation extraction that realization roasting pretreatment relates to weight dangerous waste is valuable to realize
The accumulation of metal is enriched with.
2. a kind of raising as described in claim 1 relates to weight dangerous waste bioleaching-regeneration enrichment efficiency method, feature exists
In: additive involved in step 2 include silica, sulphur, sodium sulfite, sodium thiosulfate, calcium chloride, sodium chloride,
The weight percent for accounting for material is 1.0%-10%.
3. a kind of raising as described in claim 1 relates to weight dangerous waste bioleaching-regeneration enrichment efficiency method, feature exists
In: Muffle furnace atmosphere is air or air and the compound atmosphere of vapor, and it is 0.25 liter -2.5 that air and vapor, which are passed through rate,
Liter/min.
4. a kind of raising as described in claim 1 relates to weight dangerous waste bioleaching-regeneration enrichment efficiency method, feature exists
In: the heating rate of Muffle furnace is 5-10 DEG C/min when roasting in step 2.
5. a kind of raising as described in claim 1 relates to weight dangerous waste bioleaching-regeneration enrichment efficiency method, feature exists
In: the inoculum concentration of Thiobacillus thioxidans, Thiobacillus ferrooxidans and leptospirillum ferriphilum is 2.5%-10%, v/ in step 3
v。
6. a kind of raising as described in claim 1 relates to weight dangerous waste bioleaching-regeneration enrichment efficiency method, feature exists
In: culture solution includes: KH in step 32PO4,0.5-2.0g/L；Na2HPO4,0.5-2.0g/L；KNO3, 0.5-2.0g/L；
(NH4)2SO4, 0.5-2.0g/L；NaCl, 0.5-2.0g/L；MgSO4.7H2O, 0.25-1.0g/L；CaCl2, 0.25-1.0g/L；
Na2S2O3, 4.0-24.0g/L；Sulphur or sulphur cream or sludge containing sulphur, 4.0-24.0g/L；Pyrite, 4.0-24.0g/L.
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Cited By (4)
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|---|---|---|---|---|
| CN113528831A (en) * | 2021-07-12 | 2021-10-22 | 北京建筑大学 | Method for maximum recovery of valuable metals in critical waste and standard-reaching detoxification of residues |
| CN113584316A (en) * | 2021-08-03 | 2021-11-02 | 苏州镕鑫城环保科技有限公司 | Electroplating sludge treatment equipment and treatment process based on bioleaching technology |
| CN113584317A (en) * | 2021-08-03 | 2021-11-02 | 苏州镕鑫城环保科技有限公司 | Valuable metal extraction process suitable for electroplating sludge |
| CN114634246A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Method for deep denitrification by utilizing sulfur paste autotrophic nitrogen |
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| CN114634246A (en) * | 2022-04-15 | 2022-06-17 | 合肥工业大学 | Method for deep denitrification by utilizing sulfur paste autotrophic nitrogen |
| CN114634246B (en) * | 2022-04-15 | 2024-02-02 | 合肥工业大学 | Autotrophic deep denitrification method utilizing sulfur paste |
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