CN105648224B - A kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound - Google Patents
A kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound 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
- 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
- C22B7/007—Wet processes by acid leaching
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- C22B34/32—Obtaining chromium
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Abstract
Extracted the invention provides a kind of chromium and harmful waste administers the method for reclaiming and preparing chromium compound, belong to hydrometallurgy and resource reclaim field.The present invention, first with acidleach, makes chromium, iron, three kinds of elements of aluminium fully dissolve, is filtrated to get filtrate using solid containing chromium as raw material；Under mildly acidic conditions, reducing agent selective reduction is added, Cr VI is completely converted into trivalent chromium；Then pH value of solution is adjusted, oxidant selective oxidation is added, ferrous iron is completely converted into ferric iron；One is placed in reactor, and cryogenic thermostat hydro-thermal is for a period of time；Reacted product is filtered, washed, is dried, filter cake and filtrate is obtained.Filter cake is sediment containing Fe, and cleaning solution, which is returned, to be reused.Filtrate pH is adjusted, hydrated agent is added, high temperature constant temperature hydro-thermal for a period of time, obtains compound containing Cr, and washing, dry, roasting obtain chromium oxide.Filtrate and cleaning solution pH are adjusted, solid containing Al is obtained, wash liquid liquid is reused.
Description
Technical field
The invention belongs to hydrometallurgy and the field of resource reclaim, and in particular to one kind is using chrome ore, containing chromiun intermediants
The processing method of the chromium compound served many purposes is produced with chromed leather wastes.
Background technology
Chromium has the features such as molten, boiling point is high, hardness is big, corrosion resistance is strong, and chrome green is a kind of wide variety of many
With product, it is widely used in fields such as chemical industry, refractory material and metal materials.But at present in the world the most of quality of chromium resource compared with
It is low, and the various discarded chromium that contain are harmful to waste residue.The waste residue of especially Cr VI not only causes water pollution, and soil pollution causes grain
The contamination hazard of food and whole food chain is very big.There is the producer of about 20 plus production sodium dichromate in current China, a large amount of due to producing
Offal treatment it is improper, cause sizable waste.The Cr VI contained is a kind of element for seriously endangering health,
And it is water-soluble preferably, when solid slag is largely stacked, due to rain drop erosion, can cause substantial amounts of environmental pollution.
But trivalent chromium is a kind of relatively small element of toxicity, but also it is a kind of trace element necessary to human body, if will contain
The waste residue of a large amount of Cr VIs is converted into trivalent chromium, for corresponding aspect, then has very big prospect.Therefore, how low-grade
Chrome ore and intermediate product green extraction of chromium reduce bazardous waste, and have from chromium residue synthetical recovery chromium resource actual
Meaning.
At present, there are two kinds of magnetic method and electrical concentration for chromite, the former requires that iron therein has ferromagnetism, but actual raw
It is difficult to meet this condition in work, electric separation can meet weak Magnetic Isolation, but treating capacity is small, and cost is high, therefore scale is difficult to scale up
(Tang Xiaoling, Zhu Xiali are a kind of to separate ferrochrome in chromite by magnetizing roast, China, ZL.201310475068.0).
During with acid treatment chromite and ferrochrome slag, substantial amounts of iron ion is had in leachate, influence is reclaimed, the matter of enrichment chromium
Amount, therefore, must be driven off iron therein before waste liqouor.2005, Dahnke et al. existed《Iron Control in
Hydrometallurgy》The method for proposing to be removed iron from acidic aqueous solution using phosphoric acid precipitates method, research is pointed out at 25~57 DEG C
In the range of, temperature is not obvious on the heavy iron influence of phosphoric acid, and being precipitated as being formed at room temperature is unformed, and in 50 DEG C of temperatures above bars
Gained sediment then has the crystal formation of similar phosphorus ferrosilite natural minerals under part.Li Xue in 2006 flies to use phosphonic acids kind of extractants
(such as P204) under the conditions of solution ph is 1.5 and necessarily compares extraction time, iron extraction yield is up to more than 99% but chromium simultaneously
Extraction yield also be up to 25%.Hu Guorong in 2007 delivers patent and proposes goethite process being applied to acid solution except iron and reclaim
Chromium, although the clearance of iron is up to 99%, but chromium loss rate is also higher by 15%, but also very likely results in the secondary pollution of chromium.
King parent is violent according to the relatively low (K of ferrous oxalate solubility product within 2011sp=2.1 × 10-7, 25 DEG C) property, make the iron in solution with grass
Sour ferrous state Precipitation.For oxalic acid sinks iron, in addition to temperature and pH value, oxalic acid addition is another pass of this method
Key factor.If oxalic acid addition is too low, ferrous ion is difficult to precipitation completely, if addition is excessive, and excessive oxalate will
Occurs complex reaction with ferrous oxalate, the iron ion precipitated dissolves and rework solution again, the clearance of iron is not risen instead
Drop.Although the ferrous oxalate precipitation method can realize that chromium, iron are efficiently separated, technical process is simple and easily operated, and product is oxalic acid
Ferrous and chrome green powder, but the technique need to strictly control oxalic acid addition, and be limited in pH value condition, solution and negative
Lotus is heavier.Xu Zhi peaks in 2015 etc. exist《Non-ferrous metal scientific and engineering》In point out, to the chromium in solution, iron ion phosphoric acid
The precipitation method are separated, and the concentration of chromium in solution after precipitation is down to 0.04g/L or so, and iron content is down in heavy chromium slag
0.4%.
In solid waste, chromium aluminium slag is a kind of pollutant of important metallurgical process.Deng Xiangyi etc. is in nineteen ninety-five《Hubei
Work》Chromium-contained aluminum mud process is handled in 3rd phase " recovery of chromium in waste material aluminium mud " text and utilizes polyacrylamide macromolecule precipitation of aluminium,
Cr VI can enter the purpose that solution reaches separation chromium aluminium；This method is widely used for chromium metallurgical process at present, due to precipitation
Alumine hydroxide colloid adsorptivity it is very strong, high containing chromium, separation is low, and the raising and new material especially with environmental standard are miscellaneous
The raising of matter control accuracy is difficult to meet current requirement.Li Li et al. existed in the 4th phase in 2010《Process engineering journal》" fused salt
Improved method is proposed in the separation of chromium aluminium and alkali lye circulation of method activation process red soil nickel ore leaching liquid containing a chromium " text, is utilized
Hot water is washed, and improves chromium aluminium separation；In the method implementation process, due to use substantial amounts of water washing operations, it can produce
Raw unnecessary chromyl waste water, causes secondary pollution, and environmental pollution is serious, and in alkali soluble chromium aluminium, can consume a large amount of
Highly basic, cause a part of waste.Also a kind of separation method is to add highly basic into chromium aluminium slag, makes chromium, aluminium all with ion shape
Formula exists in solution, and adds H2O2Stirring, boils, trivalent chromium is all oxidized into Cr VI, then adds dodecyl sulphur
The surfactants such as sour sodium, and acid adding adjusts pH value of solution to being sufficiently formed Al (OH)3Precipitation, filter, wash, be dried to obtain it is high-purity
Aluminum hydroxide solid, Cr VI (Chinese patent in the filtrate and washing lotion of collection：201310294122.1,2013,07~
12.).Lin Sheng etc. was the 5th phase in 2014《Mining metallurgical engineering》" from aluminothermic process prepare crome metal obtained chromium residue in reclaim chromium, aluminium technique
Roasting-water logging-carbonation decomposition-concentration and crystallization process in molten caustic soda is proposed in a research " text and produces crome metal from aluminothermic process
The method that aluminum oxide and sodium chromate are reclaimed in gained clinker, inquired into chromium slag particle degree, alkaline residue ratio, roasting time and temperature etc. because
Influence of the element to chromium and aluminium leaching rate.The leaching rate of chromium and aluminium increases and increased with alkaline residue ratio, roasting time and sintering temperature,
Reduce and increase with chromium slag particle degree, optimal extract technology condition is：700 DEG C of sintering temperature, roasting time 4h, granularity 0.045mm
With alkali ore deposit ratio 6: 1.The purity of gained chromic salts (in terms of sodium dichromate) and aluminum oxide is respectively 88.5% and 95.4%, overall recovery
85.6% and 96.4% are respectively reached, sodium is recycled in the form of sodium carbonate and sodium acid carbonate.Small refined et al. 2008 of Lee exists
《Transactions of Nonferrous Metals Society of China》" New technology on 18th phase
for comprehensive utilization of aluminum-chromium residue from chromium
Mention, the correct amounts such as chromium aluminium slag, water, additive are added in autoclave, 70 in the texts of salts production " one
Recrystallization reaction 1~2 hour, then takes out and is cooled to room temperature at~80 DEG C, filtering, washing, obtains Chrome-free aluminium slag, realizes chromium aluminium
Separation.C.Capdevila et al. 2008 exists《Journal of Materials Science》On " the Aluminum that delivers
Mentioned in the texts of partitioning during phase separation in Fe-20%Cr-6%Al ODS alloy " one,
Chromium aluminium is separated with the method for phase separation.
It is the presence of Cr VI always that to sum up chromium process is extracted and reclaimed to its subject matter, separative efficiency is not high cause it is stagnant in slag
The weak point such as stay.No matter how Cr VI is converted into trivalent chromium in extraction process or solid waste waste liqouor process, then with letter
Single method prepares chromium trioxide and realizes that the method for the two separation then has very big prospect, yet there are no report.
The content of the invention
The purpose of the present invention be overcome above-mentioned not enough problem there is provided one kind using hydrothermal reduction atmosphere reduction of hexavalent chromium or
Suppress the method that Cr VI is produced, the method to carry out heavy chromium separation chromium aluminium and ferrochrome impurity is mainly characterized by without sexavalence
The procedure extraction chromium of chromium first switchs to Cr VI in waste residue to be separated after trivalent chromium.Then regulation pH adds reducing agent to make sexavalence
Chromium is converted into trivalent chromium entirely, then adjusts selective oxidation to reach only by ferrous oxidising for ferric purpose, by hydro-thermal
After reaction, separation is tapped a blast furnace, then adjusts pH, is added appropriate hydrated agent, is handled through hydrothermal deposition chromium, after filtering, acid wash liquid washing
It can obtain and contain aluminium ion in chromium oxide crystal, washing lotion, it is that can obtain aluminium hydroxide to control suitable acidity, realize chromium aluminium point
From the method for the comprehensive utilization of the purification with chromium, recovery and waste resource, flow is simple, and reaction speed is fast, and impurity is few, and waste water gives up
Gas discharge is few, environmental friendly, and obtained chromium oxide can do photoelectric semiconductor material, for smelting ferrochrome or by purification processes life
Production degree chromated oxide.
Technical scheme：
A kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound, and step is as follows：
It is broken to solid containing chromium first, chromium, three kinds of elements of iron and aluminium are contained in solid containing chromium；Wherein each member is dissolved in acidleach
Element, it is 0.5~4.5 to reach terminal pH；The insoluble matter in above-mentioned acid solution is filtered, solution will be obtained after filtering as raw material；To mistake
Filtering obtained insoluble matter, repeatedly processing to chromium content meets national environmental standard, and acid solution used repeats to make in above process
With；
PH to 0.5~6.0 is adjusted to above-mentioned raw materials, reducing agent is added, Cr VI is completely converted into trivalent chromium, then adjust
PH obtains separating ferrochrome qualifying liquid to 1.0~5.0；Oxidant is added into separation ferrochrome qualifying liquid, ferric iron, trivalent is obtained
The mixed solution of chromium and trivalent aluminium；Low-temperature hydrothermal：Under 50~150 DEG C of temperature conditionss, pressure is 0.50MPa~2.5MPa conditions
Under, incubation water heating reacts 0.5~10 hour, and along with being stirred continuously during reaction, reaction is filtrated to get filtrate with containing Fe after terminating
Sediment, regulation filtrate pH is 0.5~3.5, obtains heavy chromium qualifying liquid；High temperature hydro-thermal：Heavy chromium qualifying liquid is placed in hydrated agent close
Hydro-thermal reaction in reactor is closed, 150 DEG C~300 DEG C are heated up to, pressure is incubated 1~5 hour between 0.5MPa~3.5MPa,
To product filtering after reaction, with subacidity liquid scrubbing, drying, green filter cake, as compound containing Cr are obtained, through 500~
Chromium oxide solid is converted into after 1200 DEG C of roastings, the photoelectric materials such as semiconductor are used as.
The filtrate regulation pH obtained after high-temperature water is hankered filtering and washed is 7.0~9.5, and obtained solid containing Al is done
Dry, roasting obtains aluminum oxide.
By the sediment containing Fe obtained in low-temperature hydrothermal, it is changed into iron oxide red as iron oxide after high temperature dehydration.
Described reducing agent selects sodium sulfite, hydrogen peroxide, Fe2+Or high COD organic wastewater.
Described oxidant selects oxygen, air, hydrogen peroxide, ozone or sulphuric acid free radical.
Described hydrated agent selects oxalic acid, cellulose, methanol, formaldehyde, formic acid, ethanol or glucose.
To the subacidity liquid of the product washing after high-temperature water heat filtering, the diluted acid from pH 3.0~5.0.
During the pH of above acidleach solid containing chromium and regulation solution, from organic acid and/or inorganic acid；It is molten adjusting
During liquid pH, using cationic ion membrane electrolysis.
Cleaning solution in above procedure is reused.
Beneficial effects of the present invention：This method, which is respectively adopted selective reduction and choice oxidation process and combines hydro-thermal, carries out chromium
Extract, reclaim, the rate of heavy chromium is higher, and good separating effect, flow is simple, and reaction speed is fast, reduces the discharge of the three wastes, green ring
Protect.
Brief description of the drawings
Fig. 1 is the basic flow sheet that chromium is extracted and reclaimed.
Fig. 2 is the phenograms of SEM containing chromium compound obtained after high temperature hydro-thermal.
Fig. 3 is the phenograms of TEM containing chromium compound obtained after high temperature hydro-thermal.
Fig. 4 is the chromium oxide SEM phenograms obtained containing chromium compound after fired.
Fig. 5 is the chromium oxide TEM phenograms obtained containing chromium compound after fired.
Fig. 6 is the chromium oxide HRTEM phenograms obtained containing chromium compound after fired.
Fig. 7 be containing chromium compound with its be calcined after obtained chromium oxide XRD phenograms.
Fig. 8 is the uv absorption spectra of the chromium oxide obtained after being calcined.
Fig. 9 is the fluorescent characteristic figure of the chromium oxide obtained after being calcined, excitation wavelength lambda=246nm.
Embodiment
The present invention is described in further detail with reference to technical scheme and accompanying drawing, but the invention is not limited in specific
Embodiment.
Example 1：Ferrochrome is raw material
Material composition is as follows：
The high carbon ferro-chrome composition of table 1
15.0g high carbon ferro-chromes are taken, 35mL volume fractions 60% are dissolved in in sulfuric acid solution, heating water bath to 80 DEG C, constant temperature
30min, makes it fully react.Then room temperature is cooled to, a small amount of insoluble matter is filtered out, obtains mixed containing chromium, iron and other impurities
Solution filtrate is closed, 10 times are diluted, its pH to 2.8 is adjusted for 5% sulfuric acid with mass fraction.The 10mL filtrates are taken, are added
2mL mass fractions are 20% hydrogen peroxide, stir 30min, are subsequently placed in 18mL closed reactor, under the conditions of 90 DEG C
Constant temperature 2 hours, is cooled to room temperature, filtering, obtains sediment containing Fe and green filtrate.Methanol 1.5mL is added in the filtrate, is used
The sulphur acid for adjusting pH of mass fraction 5% is placed in 18mL closed reactor to 2.1, constant temperature 1.5 hours under the conditions of 210 DEG C,
Room temperature is cooled to, is filtered, deionized water is washed, is calcined 3.5 hours at being dried 2 hours, 600 DEG C at 120 DEG C, obtains green oxidation
Chromium crystal (Characterization of The Products is as shown in Fig. 2~Fig. 9).Sediment containing Fe is obtained in ferric oxide solid, said process after being calcined through 500 DEG C
Filtrate and cleaning solution are reused.
Example 2：Castaway slag containing chromium is raw material
The chromium aluminium slag composition of table 2
10.0g chromium aluminium slags are taken, 20mL volume fractions 13% are dissolved in in sulfuric acid solution, heating response 35min so that chromium aluminium
Slag reaction is complete.Reacted material is filtered, filtrate is obtained, 5 times are diluted, it is 20% to add 0.5mL mass fraction
Hydrogen peroxide, stirs 30min, obtains green solution.Solution 10mL is taken, 1.5mL methanol is added, pH to 1.9, Ran Houjia is adjusted
Enter and reacted 2 hours at the closed reactor to 18mL, 140 DEG C.After reaction terminates, room temperature is cooled to, is filtered, is 3.5 with pH
Oxalic acid is washed three times to solid, and obtained solid is dried at 110 DEG C and is calcined 2.5 hours at 2 hours, 450 DEG C, obtains chromium oxide
Crystal.To the filtrate being collected into and cleaning solution, its pH being adjusted to 8, white precipitate is obtained, filtered, deionized water washing is dried,
It is calcined 2.5 hours at 300 DEG C, obtains filtrate and cleaning solution in alumina solid, said process and may be reused.
Example 3：A kind of chrome ore is raw material
The chrome ore composition of table 3
15.0g chrome ores are taken, 30mL volume fractions 45% are dissolved in in sulfuric acid solution, heating water bath to 80 DEG C, constant temperature
30min, makes chrome ore fully react.Then room temperature is cooled to, a small amount of insoluble matter is filtered out, obtained containing chromium, iron and other impurities
Mixed solution filtrate, its pH to 2.8 is adjusted with cationic membrane electrolysis.Take the 10mL filtrates, under conditions of stirring, be passed through smelly
Oxygen 10min completes selective oxidation, is subsequently placed in 18mL closed reactor, constant temperature 1 hour under the conditions of 90 DEG C, then cool down
To room temperature, filtering obtains sediment containing Fe and green filtrate.Methanol 1.5mL is added in green filtrate, cationic membrane electrolysis is used
PH to 2.1 is adjusted, is placed in 18mL closed reactor, constant temperature 1.5 hours at 210 DEG C are cooled to room temperature, filters, spends
Ion water washing, is calcined 3 hours at drying 2 hours, 500 DEG C at 120 DEG C, obtains chromium oxide crystal.To the filtrate that is collected into and
Cleaning solution, adjusts its pH to 8, obtains white precipitate, filtering, deionized water washing, dries, is calcined 2.5 hours, obtains at 300 DEG C
To alumina solid, filtrate and cleaning solution may be reused in said process.
Claims (10)
1. a kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound, it is characterised in that step is as follows：
It is broken to solid containing chromium first, chromium, three kinds of elements of iron and aluminium are contained in solid containing chromium；Acidleach dissolving wherein each element, reaches
It is 0.5~4.5 to terminal pH；The insoluble matter in acid solution after acidleach is filtered, solution will be obtained after filtering as raw material；To filtering
To insoluble matter repeatedly processing meets national environmental standard to chromium content, acid solution used is reused in above process；
PH to 0.5~6.0 is adjusted to above-mentioned raw materials, reducing agent is added, Cr VI is completely converted into trivalent chromium, then adjust pH to
1.0~5.0, obtain separating ferrochrome qualifying liquid；To separation ferrochrome qualifying liquid in add oxidant, obtain ferric iron, trivalent chromium and
The mixed solution of trivalent aluminium；Low-temperature hydrothermal：Under 50~150 DEG C of temperature conditionss, pressure be 0.50MPa~2.5MPa under the conditions of,
Incubation water heating reacts 0.5~10 hour, and along with being stirred continuously during reaction, reaction is filtrated to get filtrate with being sunk containing Fe after terminating
Slag, regulation filtrate pH is 0.5~3.5, obtains heavy chromium qualifying liquid；High temperature hydro-thermal：Heavy chromium qualifying liquid is placed in hydrated agent closed
Hydro-thermal reaction in reactor, is heated up to 150 DEG C~300 DEG C, and pressure is incubated 1~5 hour between 0.5MPa~3.5MPa, right
Product filtering after reaction, with subacidity liquid scrubbing, drying, green filter cake is obtained, as compound containing Cr, through 500~1200
DEG C roasting after be converted into chromium oxide solid；
The filtrate regulation pH obtained after high-temperature water is hankered filtering and washed is 7.0~9.5, and obtained solid containing Al is dried, roasted
Burning obtains aluminum oxide；
By the sediment containing Fe obtained in low-temperature hydrothermal, it is changed into iron oxide red as iron oxide after high temperature dehydration.
2. according to the method described in claim 1, it is characterised in that described reducing agent selects sodium sulfite, hydrogen peroxide, Fe2 +Or high COD organic wastewater.
3. method according to claim 1 or 2, it is characterised in that described oxidant selects oxygen, air, peroxidating
Hydrogen, ozone or sulphuric acid free radical.
4. method according to claim 1 or 2, it is characterised in that described hydrated agent from oxalic acid, cellulose, methanol,
Formaldehyde, formic acid, ethanol or glucose.
5. method according to claim 3, it is characterised in that described hydrated agent selects oxalic acid, cellulose, methanol, first
Aldehyde, formic acid, ethanol or glucose.
6. the method according to claim 1,2 or 5, it is characterised in that to the product washing after high-temperature water heat filtering
Subacidity liquid, the diluted acid from pH 3.0~5.0.
7. method according to claim 3, it is characterised in that to the subacidity of the product washing after high-temperature water heat filtering
Liquid, the diluted acid from pH 3.0~5.0.
8. method according to claim 4, it is characterised in that to the subacidity of the product washing after high-temperature water heat filtering
Liquid, the diluted acid from pH 3.0~5.0.
9. the method according to claim 1,2,5,7 or 8, it is characterised in that molten in above acidleach solid containing chromium and regulation
During the pH of liquid, from organic acid and/or inorganic acid；When adjusting pH value of solution, using cationic ion membrane electrolysis.
10. method according to claim 6, it is characterised in that in the pH mistakes of above acidleach solid containing chromium and regulation solution
Cheng Zhong, from organic acid and/or inorganic acid；When adjusting pH value of solution, using cationic ion membrane electrolysis.
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| CN201610179512.8A CN105648224B (en) | 2016-03-25 | 2016-03-25 | A kind of chromium is extracted and harmful waste administers the method for reclaiming and preparing chromium compound |
| US15/776,985 US11071967B2 (en) | 2016-03-25 | 2017-03-02 | Method of preparation and application of ion-keeper adsorbent |
| PCT/CN2017/075455 WO2017162013A1 (en) | 2016-03-25 | 2017-03-02 | Preparation and application method for ion blocking and controlling adsorbent |
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| CN106699027B (en) * | 2016-12-07 | 2018-10-23 | 云南大地绿坤环保科技有限公司 | A kind of processing method of chromium residue |
| CN107419105B (en) * | 2017-07-25 | 2018-08-17 | 盛隆资源再生（无锡）有限公司 | A method of iron, copper, nickel, chromium in classification recycling electroplating sludge |
| CN109289759B (en) * | 2018-11-23 | 2021-06-18 | 张少强 | Solid alkali adsorbent and integrated device for synchronously treating acid gas and organic waste gas |
| CN111910076B (en) * | 2019-05-09 | 2022-04-05 | 湖北振华化学股份有限公司 | Method for removing iron impurities from trivalent chromium compound |
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| CN116273018A (en) * | 2021-12-06 | 2023-06-23 | 苏州市清泽环境技术有限公司 | Al@Al based on aluminum mud hazardous waste 2 O 3 Preparation method of micro-nano catalytic material |
| CN114632509B (en) * | 2022-03-25 | 2023-04-21 | 昆明理工大学 | Preparation of Cr-Al by using aluminium-chromium slag 2 O 3 Method for preparing mesoporous catalytic material and application thereof |
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| JPS5357112A (en) * | 1976-11-02 | 1978-05-24 | Nakamichi Yamazaki | Metallurgy of chronium |
| ES2046655T3 (en) * | 1989-12-16 | 1994-02-01 | Bayer Ag | PROCEDURE FOR OBTAINING CHROMIC ACID. |
| CN101993112B (en) * | 2009-08-25 | 2012-09-26 | 中国科学院过程工程研究所 | Clean method for preparing low-sulfur chromium oxide green |
| CN101863512B (en) * | 2010-04-15 | 2011-12-28 | 彭运林 | Acid method recycling process of chromium-containing aluminum mud |
| CN102690953B (en) * | 2011-03-19 | 2014-02-26 | 渤海大学 | Method for preparing compound powder of alumina and chrome oxide from chromium-containing aluminum sludge |
| CN102826605B (en) * | 2012-09-11 | 2014-05-14 | 电子科技大学 | Preparation method for chromium oxide nanometer materials |
| CN103225131B (en) * | 2013-05-06 | 2015-04-08 | 渤海大学 | Al2O3, Cr2O3 composite nanofiber or nanosheet prepared from chromium-bearing aluminium sludge and preparation method thereof |
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