CN104291540B - A kind of recycling processing method of red mud - Google Patents
A kind of recycling processing method of red mud Download PDFInfo
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- CN104291540B CN104291540B CN201410056901.2A CN201410056901A CN104291540B CN 104291540 B CN104291540 B CN 104291540B CN 201410056901 A CN201410056901 A CN 201410056901A CN 104291540 B CN104291540 B CN 104291540B
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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
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a kind of recycling processing method of red mud, comprising: 1) red mud is added in soda ash solution and carry out causticizing reaction, filter to obtain filter cake A; 2) added in hydrochloric acid by filter cake A and carry out acidolysis reaction, filter to get filtrate B; 3) in liquor B, add hydrogen peroxide solution and carry out oxidizing reaction, then add phosphoric acid and carry out neutralization reaction, filter to get filtrate C; 4) in liquor C, add sodium sulfide solution and carry out precipitin reaction, filter to get filtrate D; 5) in filtrate D, add caustic soda soln and carry out neutralization reaction, filter to get filtrate E; 6) in filtrate E, add ammoniacal liquor and carry out neutralization reaction, filter to get filtrate F; 7) in filtrate F, add caustic soda soln and carry out precipitin reaction, filter to get filtrate G; 8) in filtrate G, add hydrochloric acid, after evaporation, crystallization, filter to obtain filter cake H.Treatment process of the present invention, achieves recycling treatment and the comprehensive reutilization of red mud, has good economic benefit, environmental benefit and social benefit.
Description
Technical field
The invention belongs to Using Metallurgical Solid Wastes recovery technology field, be specifically related to a kind of recycling processing method of red mud.
Background technology
Red mud is the solid waste of discharging in aluminum oxide metallurgy industry production process, gains the name because its appearance color is similar to red mud with form.Red mud is overbased material, and complex chemical composition is as shown in table 1.
Table 1 red mud chemical composition (unit: %)
| Area | Burning decrement | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | TiO 2 | K 2O | Na 2O |
| Shandong | 11.70 | 22.00 | 6.40 | 9.02 | 41.90 | 1.70 | 3.20 | 0.30 | 2.80 |
| Guizhou | 11.10 | 25.90 | 8.50 | 5.00 | 38.40 | 1.50 | 4.40 | 0.20 | 3.10 |
| Central Region | 16.26 | 21.36 | 8.76 | 8.56 | 36.01 | 1.86 | 2.64 | 0.77 | 3.21 |
| Shanxi | 8.00 | 21.43 | 8.22 | 8.12 | 46.80 | 2.03 | 2.90 | 0.20 | 2.60 |
| On average | 11.77 | 22.67 | 7.97 | 7.68 | 40.78 | 1.77 | 3.29 | 0.38 | 2.93 |
Note: 1. in addition, the element compounds such as the copper also containing trace, vanadium, zirconium, niobium, manganese, zinc, boron, thorium and rare earth;
2. " Central Region " in upper table is former Central Region aluminium manufacturer, is positioned at Jiaozhuo.
Under normal circumstances, 1t aluminum oxide about output 1.0 ~ 1.8t red mud is often produced.Within 1999, China's aluminum oxide output is 383.7 ten thousand tons, average annual progressive increase rate 15.7%, estimates that China's aluminum oxide metallurgy industry in 2010 is by about nearly for output red mud 4,000 ten thousand tons.It is that current discharge capacity endangers one of serious major industry waste residue being difficult to again processing and utilizing comparatively greatly, to physical environment, the non-ferrous metal waste residue that Ye Shi China quantity is maximum.So far, generally still take to stack process to the process of red mud.China's various places alumina producer generally adopts the methods such as build a dam in level land, dam, hurdle, river valley, lowland filling to stack process.Due to safeguard procedures imperfection, cause red mud waste liquid polluted underground water, local water source is forever alkalized.Stack process and both wasted a large amount of soil of storeyard, very easily cause again contaminate environment such as " reentrainment of dusts ".The red mud of a large amount of discharge takies a large amount of soil for a long time, causes soil to alkalize and atmospheric pollution, causes direct or indirect harm to human being's production, life.Along with day by day increasing and people's improving constantly environmental protection consciousness of red mud discharge capacity, accelerate the recycling treatment of red mud, make full use of national resources; limit the harm that red mud produces to greatest extent; reduce floor space, protection of the environment, has become the significant problem and a difficult problem that must conscientiously solve.
At present red mud is carried out to research and the technological development of some related resources process, as: extract iron by red mud; Cement and other material of construction is produced with red mud; As road-making material, Mine ventilator material; Plastics additive is made with red mud; The added ingredients of siliceous fertilizer is made of red mud; The sorbent material etc. of wastewater treatment is made with the red mud after process.These treatment processs utilize red mud limited amount, and are simple process mostly, be only make use of one or more valuable constituents in red mud, and the valuable constituent do not made full use of in red mud carry out recycling treatment; Meanwhile, after such simple process, mostly produce secondary solid waste, cause more serious environmental pollution.Therefore, absorb new scientific and technological achievement, change the design concept of traditional just process and process, adopt innovation design idea and innovative design technology, recycling treatment is carried out to red mud, turns waste into wealth, save national resources, reduce environmental pollution, be alumina producing enterprise, society and country common in the urgent need to.
Summary of the invention
The object of this invention is to provide a kind of recycling processing method of red mud, solve existing red mud recycling treatment and fully can not reclaim valuable constituent, easily produce the problem of secondary pollution simultaneously.
In order to realize above object, the technical solution adopted in the present invention is: a kind of recycling processing method of red mud, comprises the following steps:
1) red mud is added in soda ash solution, be heated to 60 ~ 100 DEG C and carry out causticizing reaction, after reaction, filter to obtain filter cake A;
2) filter cake A is added in hydrochloric acid, be heated to 40 ~ 80 DEG C and carry out acidolysis reaction, after reaction, filter to obtain filter cake B and liquor B;
3) in liquor B, add hydrogen peroxide solution, carry out oxidizing reaction under room temperature condition, after reaction, add phosphoric acid again, be heated to 60 ~ 100 DEG C and carry out neutralization reaction, after reaction, regulate reaction system pH to be 1.5 ~ 2.0, after insulation reaction, filter to obtain filter cake C and liquor C, described filter cake C is tertiary iron phosphate crude product;
4) in liquor C, add sodium sulfide solution, regulation system pH is 2.5 ~ 3.0, is heated to 50 ~ 95 DEG C and carries out precipitin reaction, and filter to obtain filter cake D and filtrate D after reaction, described filter cake D is cupric sulfide crude product;
5) in filtrate D, add caustic soda soln, regulation system pH is 3.5 ~ 5.5, is heated to 60 ~ 100 DEG C and carries out neutralization reaction, and filter to obtain filter cake E and filtrate E after reaction, described filter cake E is aluminium hydroxide crude product;
6) in filtrate E, add ammoniacal liquor, regulation system pH is 6.0 ~ 8.5, is heated to 30 ~ 60 DEG C and carries out neutralization reaction, filters to obtain filter cake F and filtrate F after reaction, and described filter cake F is basic zirconium chloride, hydration Niobium Pentxoxide, manganous hydroxide crude mixture;
7) in filtrate F, add caustic soda soln, regulation system pH is 10.0 ~ 12.5, is heated to 40 ~ 90 DEG C and carries out precipitin reaction, and filter to obtain filter cake G and filtrate G after reaction, described filter cake G is magnesium hydroxide crude product;
8) in filtrate G, add hydrochloric acid, the pH of regulation system is 3.5 ~ 5.5, and after evaporation, crystallization, filter to obtain filter cake H, described filter cake H is Calcium dichloride dihydrate finished product.
The time of causticizing reaction described in step 1) is 80 ~ 180min; Step 2) described in time of acidolysis reaction be 120 ~ 240min; The time of oxidizing reaction described in step 3) is 20 ~ 60min, and the time of described neutralization reaction is 120 ~ 240min, and the time of described insulation reaction is 180 ~ 300min; The time of precipitin reaction described in step 4) is 60 ~ 120min; The time of neutralization reaction described in step 5) is 60 ~ 120min; The time of neutralization reaction described in step 6) is 60 ~ 120min; The time of precipitin reaction described in step 7) is 60 ~ 120min.
The massfraction of soda ash solution described in step 1) is 9% ~ 30%.
The mass ratio of red mud described in step 1) and soda ash solution is 1:5 ~ 8.
Step 2) described in the massfraction of hydrochloric acid be 9% ~ 30%; The mass ratio of described hydrochloric acid soln and filter cake A is 8 ~ 11:1.
The massfraction of hydrogen peroxide solution described in step 3) is 12% ~ 28%; The volume ratio of described hydrogen peroxide solution and liquor B is 0.10 ~ 0.30:100.
The massfraction of phosphoric acid described in step 3) is 40% ~ 85%; The volume ratio of described phosphoric acid and liquor B is 2.0 ~ 20:100.
The method of reaction system pH is regulated to be in reaction system, add the sodium hydroxide solution that massfraction is 8% ~ 30% in step 3).
The massfraction of sodium sulfide solution described in step 4) is 5% ~ 20%; Described in step 5) and step 7), the massfraction of caustic soda soln is 8% ~ 30%; The massfraction of ammoniacal liquor described in step 6) is 8% ~ 20%; The massfraction of hydrochloric acid described in step 8) is 9% ~ 30%.
Step 2) described in filter cake B for reclaiming titanium dioxide.The method of described recovery titanium dioxide is: be the ratio of 100:8 ~ 20 according to the mass ratio of filter cake B and sulfuric acid, after filter cake B is mixed with sulfuric acid, roasting 2 ~ 4h under 400 ~ 700 DEG C of conditions, add the water with weight such as filter cake B again, under 75 ~ 95 DEG C of conditions, leach 2 ~ 4h, filter to obtain filter cake and filtrate afterwards; As building-assisted material after described filter cake washing; Described filtrate, after hydrolysis, filtering, obtains titanium dioxide.
The recycling processing method of red mud of the present invention, described filtration adopts Medium speed filter paper to filter, and preferably adopts Medium speed filter paper to carry out vacuum filtration.
The recycling processing method of red mud of the present invention, the chemical reaction related to is mainly:
Step 1):
Ca(OH)
2+Na
2CO
3=2NaOH+CaCO
3↓
ZrSiO
4+6NaOH=Na
4SiO
4+Na
2ZrO
3↓+3H
2O
Fe(NbO
3)
2+10NaOH=2Na
5NbO
5↓+FeO+5H
2O
Step 2):
CaCO
3+2HCl=CaCl
2+CO
2↑+H
2O
Fe
2O
3+6HCl=2FeCl
3+3H
2O
FeO+2HCl=FeCl
2+H
2O
CuO+2HCl=CuCl
2+H
2O
Al
2O
3+6HCl=2AlCl
3+3H
2O
MgO+2HCl=MgCl
2+H
2O
NaOH+2HCl=NaCl+H
2O
Na
2ZrO
3+4HCl=ZrOCl
2+2NaCl+2H
2O
Na
8Nb
6O
19·nH
2O+26HCl→6NbOCl
3+nH
2O+8NaCl
MnO+2HCl=MnCl
2+H
2O
Step 3):
2FeCl
2+H
2O
2+2HCl=2FeCl
3+2H
2O
FeCl
3+H
3PO
4=FePO
4↓+3HCl
H
3PO
4+NaOH=NaH
2PO
4+H
2O
NaOH+HCl=NaCl+H
2O
Step 4):
CuCl
2+Na
2S=CuS↓+2NaCl
Na
2S+2HCl=2NaCl+H
2O
Step 5):
AlCl
3+3NaOH=Al(OH)
3↓+3NaCl
NaOH+HCl=NaCl+H
2O
Step 6):
ZrOCl
2+2NH
3·H
2O→Zr(OH)
2Cl
2↓+3NH
4Cl+H
2O
2NbOCl
3+6NH
3·H
2O+(n+3)H
2O→Nb
2O
5·nH
2O↓+6HCl+6H
2O
MnCl
2+2NH
3·H
2O=Mn(OH)
2↓+2NH
4Cl+2H
2O
2NaH
2PO
4+NH
3·H
2O=Na
2HPO
4+NH
4H
2PO
4+H
2O
HCl+NH
3·H
2O=NH
4Cl+H
2O
Step 7):
MgCl
2+2NaOH=Mg(OH)
2↓+2NaCl
NH
4Cl+NaOH=NaCl+NH
3↑+H
2O
NH
4H
2PO
4+3NaOH=Na
3PO
4+NH
3↑+3H
2O
Na
2HPO
4+NaOH=Na
3PO
4+H
2O
The recycling processing method of red mud of the present invention, add soda ash and carry out causticizing reaction, calcium hydroxide in red mud is utilized to generate caustic soda, and reclaim the caustic soda contained in red mud Central Plains simultaneously, after then adopting strong acid leaching agent to leach red mud, then adopt series reaction and the separating technologies such as oxidation, neutralization, filtration, precipitation, filtration successively, the valuable metal in red mud is reclaimed in classification in batches, achieve recycling treatment and the comprehensive reutilization of red mud, turn waste into wealth, save resource; Reclaim the valuable constituent in red mud to greatest extent, it is high that gained reclaims added value of product; Solve the waste in environmental pollution that existing red mud pilling causes and a large amount of storeyard soil; Have the advantages that technical process is simple, facility investment is few, reaction conditions is gentle, production cost is low, there is good economic benefit, environmental benefit and social benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the recycling processing method of the red mud of embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The recycling processing method of the red mud of the present embodiment, comprises the following steps:
1) in the beaker that mechanical stirring and thermometer are housed, add red mud (butt) 200g, water 1360ml, open and stir and electric furnace, add soda ash 180g again, be heated to 98 DEG C and carry out causticizing reaction, after reaction 2h, stop heating, Temperature fall to 40 DEG C, vacuum filtration, obtains filter cake A and filtrate A; Described filtrate A is faint yellow settled solution, and volume is 1134ml, weight 1257g, for massfraction is about the caustic soda soln of 10%; Wash filter cake A with water 2 times, each bath water 500ml, the water after washing is micro-yellow, can be used as aforementioned causticizing reaction water after merging, and the filter cake A after washing enters step 2) process;
2) filter cake A is added in the beaker that mechanical stirring and thermometer are housed, add the technical hydrochloric acid 623ml that the water of 1275ml and massfraction are 28% again, open and stir and electric furnace, be heated to 65 DEG C and carry out acidolysis reaction, after reaction 3h, muddy slurries after acidolysis are boiled 20min, and Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake B and liquor B; Described liquor B is yellow, and volume is 710ml, and weight is 738g, enters step 3) process; Described filter cake B filters after sulfuric acid solution, obtains titanium dioxide crude product;
3) liquor B is added in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, control temperature is 45 DEG C, add the hydrogen peroxide solution 1.3ml that massfraction is 22%, oxidizing reaction is carried out under room temperature condition, 85 DEG C are warming up to after reaction 60min, add again massfraction be 85% phosphatase 11 6ml carry out neutralization reaction, after reaction 2h, add massfraction be 10% sodium hydroxide solution regulate reaction system pH be 2.0, after insulation 180min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake C and yellow liquor C; Described filter cake C is faint yellow, weight 31.2g, is tertiary iron phosphate crude product;
4) liquor C added in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, control temperature is 70 DEG C, drip massfraction be 20% sodium sulfide solution be 3.0 to system pH, after insulation reaction 1h, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake D and colourless filtrate D; Described filter cake D is black, weight 2.2g, is cupric sulfide crude product;
5) filtrate D is added in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, control temperature is 70 DEG C, dripping massfraction is the sodium hydroxide solution of 10%, regulation system pH is 5.2, is heated to 90 DEG C and carries out neutralization reaction, after reaction 1h, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake E and colourless filtrate E; Described filter cake E is white, and weight 17.8g is aluminium hydroxide crude product;
6) added by filtrate E in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, control solution is in slight boiling condition and carries out atmospheric evaporation, until liquor capacity reduces by a half, stops heating; During Temperature fall to 40 DEG C, dripping massfraction is the ammoniacal liquor of 10%, and regulation system pH is 8.2, and control temperature is 40 DEG C and carries out neutralization reaction, and suction filtration after reaction 1h, obtains filter cake F and colourless filtrate F; Described filter cake F is light grey, and weight 0.46g is basic zirconium chloride, hydration Niobium Pentxoxide, manganous hydroxide crude mixture;
7) filtrate F is added in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, control temperature is 80 DEG C, and dripping massfraction is the caustic soda soln of 10%, regulation system pH 11.2 carries out precipitin reaction, and after reaction 1h, suction filtration obtains filter cake G and colourless filtrate G; Described filter cake G is white, and weight 2.6g is magnesium hydroxide crude product;
8) filtrate G is added in the beaker that mechanical stirring and thermometer are housed, open and stir and electric furnace, to add massfraction be the pH of the hydrochloric acid regulation system of 30% is 5.5, controls solution and is in slight boiling condition and carries out atmospheric evaporation, reach till 174 DEG C until solution temperature, stop heating, during Temperature fall to 40 DEG C, suction filtration, obtains micro-yellow filter cake H, weight 230g is Calcium dichloride dihydrate finished product; Colourless permeate H manages elsewhere.
Embodiment 2
1), under agitation condition, massfraction 200g red mud being added 840ml is in the soda ash solution of 30%, is heated to 60 DEG C and carries out causticizing reaction, after reaction 180min, and Temperature fall to 40 DEG C, vacuum filtration, obtains filter cake A and filtrate A; Described filtrate A is the caustic soda soln that massfraction is about 8.9%, and filter cake A carry out step 2 after washing 2 times) process;
2) under agitation condition, filter cake A is joined 1770ml, massfraction is in the hydrochloric acid of 10%, be heated to 80 DEG C and carry out acidolysis reaction, after reaction 120min, muddy slurries after acidolysis are boiled 20min, and Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake B and liquor B; Described filter cake B filters after sulfuric acid solution, obtains silicon-dioxide crude product;
3) under agitation condition, in the liquor B of 605ml, add 1.5ml, massfraction is the hydrogen peroxide solution of 22%, oxidizing reaction is carried out under room temperature condition, reaction 40min after be warming up to 60 DEG C, then add 24ml, massfraction be 85% phosphoric acid carry out neutralization reaction, reaction 180min after, add massfraction be 30% sodium hydroxide solution regulate reaction system pH be 1.5, after insulation 240min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake C and yellow liquor C; Described filter cake C is faint yellow, weight 32.3g, is tertiary iron phosphate crude product;
4) under agitation condition, in liquor C, add the sodium sulfide solution that massfraction is 5%, regulation system pH is 2.5, is heated to 95 DEG C and carries out precipitin reaction, and after reaction 90min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake D and colourless filtrate D; Described filter cake D is black, weight 2.3g, is cupric sulfide crude product;
5) under agitation condition, in filtrate D, add the caustic soda soln that massfraction is 30%, regulation system pH is 4.5, is heated to 80 DEG C and carries out neutralization reaction, and after reaction 90min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake E and colourless filtrate E; Described filter cake E is white, and weight 17.2g is aluminium hydroxide crude product;
6) under agitation condition, the ammoniacal liquor that massfraction is 20% is added in filtrate E, regulation system pH is 7.0, be heated to 60 DEG C and carry out neutralization reaction, after reaction 90min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake F and filtrate F, and described filter cake F is light grey, weight 0.45g is basic zirconium chloride, hydration Niobium Pentxoxide, manganous hydroxide crude mixture;
7) under agitation condition, the caustic soda soln that massfraction is 20% is added in filtrate F, regulation system pH is 10.0, be heated to 90 DEG C and carry out precipitin reaction, after reaction 90min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake G and filtrate G, and described filter cake G is white, weight 2.6g is magnesium hydroxide crude product;
8) under agitation condition, in filtrate G, add massfraction be the pH of the hydrochloric acid regulation system of 20% is 4.0, control solution is in slight boiling condition and carries out atmospheric evaporation, reach till 174 DEG C until solution temperature, stop heating, during Temperature fall to 40 DEG C, suction filtration, obtaining micro-yellow filter cake H, weight 229g, is Calcium dichloride dihydrate finished product; Colourless permeate H manages elsewhere.
Embodiment 3
1), under agitation condition, massfraction 200g red mud being added 1310ml is in the soda ash solution of 20%, is heated to 80 DEG C and carries out causticizing reaction, after reaction 80min, and Temperature fall to 40 DEG C, vacuum filtration, obtains filter cake A and filtrate A; Described filtrate A is the caustic soda soln that massfraction is about 9.4%, and filter cake A carry out step 2 after washing 2 times) process;
2) under agitation condition, filter cake A is added 1570ml, massfraction is in the hydrochloric acid of 30%, be heated to 40 DEG C and carry out acidolysis reaction, after reaction 240min, the muddy slurries after acidolysis are boiled 20min, and Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake B and liquor B; Described filter cake B filters after sulfuric acid solution, obtains silicon-dioxide crude product;
3) under agitation condition, in 570ml liquor B, add 1.5ml, massfraction is the hydrogen peroxide solution of 28%, oxidizing reaction is carried out under room temperature condition, reaction 20min after be warming up to 100 DEG C, then add 26ml, massfraction be 85% phosphoric acid carry out neutralization reaction, reaction 240min after, add massfraction be 20% sodium hydroxide solution regulate reaction system pH be 2.0, after insulation 300min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake C and yellow liquor C; Described filter cake C is faint yellow, weight 29.1g, is tertiary iron phosphate crude product;
4) under agitation condition, in liquor C, add the sodium sulfide solution that massfraction is 15%, regulation system pH is 3.0, is heated to 50 DEG C and carries out precipitin reaction, and after reaction 120min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake D and colourless filtrate D; Described filter cake D is black, weight 2.1g, is cupric sulfide crude product;
5) under agitation condition, in filtrate D, add the caustic soda soln that massfraction is 20%, regulation system pH is 3.5, is heated to 60 DEG C and carries out neutralization reaction, and after reaction 120min, Temperature fall to 40 DEG C carries out suction filtration, obtains filter cake E and colourless filtrate E; Described filter cake E is white, and weight 9.1g is aluminium hydroxide crude product;
6) under agitation condition, the ammoniacal liquor that massfraction is 15% is added in filtrate E, regulation system pH is 6.0, be heated to 30 DEG C and carry out neutralization reaction, carry out suction filtration after reaction 120min, obtain filter cake F and filtrate F, described filter cake F is light grey, weight 0.41g is basic zirconium chloride, hydration Niobium Pentxoxide, manganous hydroxide crude mixture;
7) under agitation condition, the caustic soda soln that massfraction is 30% is added in filtrate F, regulation system pH is 12.5, be heated to 40 DEG C and carry out precipitin reaction, carry out suction filtration after reaction 120min, obtain filter cake G and filtrate G, described filter cake G is white, weight 132.2g is magnesium hydroxide, calcium hydroxide crude mixture;
8) under agitation condition, in filtrate G, add massfraction be the pH of the hydrochloric acid regulation system of 30% is 3.5, control solution is in slight boiling condition and carries out atmospheric evaporation, reach till 174 DEG C until solution temperature, stop heating, during Temperature fall to 40 DEG C, suction filtration, obtaining micro-yellow filter cake H, weight 128.3g, is Calcium dichloride dihydrate finished product; Colourless permeate H manages elsewhere.
Experimental example
This experimental example carries out economic analysis to the method for embodiment 1, and use the method year process 500,000 t red muds of embodiment 1, analytical results is as shown in table 1,2.
Table 1 main raw material input cost
| Material name | Input amount (ten thousand t/) | Prices current (unit/t) | Raw materials cost (ten thousand yuan) |
| Red mud (butt) | 50 | - | - |
| 96% soda ash | 49.5 | 1200 | 59400 |
| 20% hydrochloric acid | 249 | 220 | 54780 |
| 28% hydrogen peroxide solution | 0.285 | 1800 | 513 |
| Precipitation agent | 6.2 | 5100 | 31620 |
| 18% ammoniacal liquor | 0.72 | 1800 | 1296 |
| Add up to | - | - | 147609 |
General item investment: according to the estimation of scaled index method calculation formula, general item investment about 1,020,000,000 yuan.
The economic benefit of the main output product of table 2
| Name of product | Quantum of output (ten thousand t/) | Prices current (unit/t) | Economic benefit (ten thousand yuan) |
| 30% caustic soda soln | 77 | 670 | 51590 |
| 98% tertiary iron phosphate | 9.5 | 4800 | 45600 |
| 96% aluminium hydroxide | 5 | 4600 | 23000 |
| 98% titanium dioxide | 3.6 | 14000 | 50400 |
| 98% magnesiumcarbonate | 2.05 | 3200 | 6560 |
| 94% Calcium dichloride dihydrate | 57.5 | 970 | 55775 |
| Add up to | - | - | 232925 |
Except the product shown in table 2, also another output chromium cpd 395t, zirconium compounds 600t, niobium compound 70t, another byproduct sodium chloride and ammonium chloride.
Input-output space difference: 232925-147609=85316 ten thousand yuan/year.
The input-output difference space of process ton red mud (butt) is:
(85,316 ten thousand yuan × 10000)/(50 × 10000t)=1706 yuan/t.
The project static payback time is: (85316/102000)+2=2.8 year.
From above-mentioned economic analysis, recycling processing method less investment, the output of the red mud of embodiment 1 are high, and the payback period is short, illustrate that the recycling processing method of red mud of the present invention has good economic benefit, are applicable to applying.
Claims (10)
1. a recycling processing method for red mud, is characterized in that: comprise the following steps:
1) red mud is added in soda ash solution, be heated to 60 ~ 100 DEG C and carry out causticizing reaction, after reaction, filter to obtain filter cake A;
2) filter cake A is added in hydrochloric acid, be heated to 40 ~ 80 DEG C and carry out acidolysis reaction, after reaction, filter to obtain filter cake B and liquor B;
3) in liquor B, add hydrogen peroxide solution, carry out oxidizing reaction under room temperature condition, after reaction, add phosphoric acid again, be heated to 60 ~ 100 DEG C and carry out neutralization reaction, after reaction, regulate reaction system pH to be 1.5 ~ 2.0, after insulation reaction, filter to obtain filter cake C and liquor C, described filter cake C is tertiary iron phosphate crude product;
4) in liquor C, add sodium sulfide solution, regulation system pH is 2.5 ~ 3.0, is heated to 50 ~ 95 DEG C and carries out precipitin reaction, and filter to obtain filter cake D and filtrate D after reaction, described filter cake D is cupric sulfide crude product;
5) in filtrate D, add caustic soda soln, regulation system pH is 3.5 ~ 5.5, is heated to 60 ~ 100 DEG C and carries out neutralization reaction, and filter to obtain filter cake E and filtrate E after reaction, described filter cake E is aluminium hydroxide crude product;
6) in filtrate E, add ammoniacal liquor, regulation system pH is 6.0 ~ 8.5, is heated to 30 ~ 60 DEG C and carries out neutralization reaction, filters to obtain filter cake F and filtrate F after reaction, and described filter cake F is basic zirconium chloride, hydration Niobium Pentxoxide, manganous hydroxide crude mixture;
7) in filtrate F, add caustic soda soln, regulation system pH is 10.0 ~ 12.5, is heated to 40 ~ 90 DEG C and carries out precipitin reaction, and filter to obtain filter cake G and filtrate G after reaction, described filter cake G is magnesium hydroxide crude product;
8) in filtrate G, add hydrochloric acid, the pH of regulation system is 3.5 ~ 5.5, and after evaporation, crystallization, filter to obtain filter cake H, described filter cake H is Calcium dichloride dihydrate finished product.
2. the recycling processing method of red mud according to claim 1, is characterized in that: the time of causticizing reaction described in step 1) is 80 ~ 180min; Step 2) described in time of acidolysis reaction be 120 ~ 240min; The time of oxidizing reaction described in step 3) is 20 ~ 60min, and the time of described neutralization reaction is 120 ~ 240min, and the time of described insulation reaction is 180 ~ 300min; The time of precipitin reaction described in step 4) is 60 ~ 120min; The time of neutralization reaction described in step 5) is 60 ~ 120min; The time of neutralization reaction described in step 6) is 60 ~ 120min; The time of precipitin reaction described in step 7) is 60 ~ 120min.
3. the recycling processing method of red mud according to claim 1, is characterized in that: the massfraction of soda ash solution described in step 1) is 9% ~ 30%.
4. the recycling processing method of the red mud according to claim 1 or 3, is characterized in that: the mass ratio of red mud described in step 1) and soda ash solution is 1:5 ~ 8.
5. the recycling processing method of red mud according to claim 1, is characterized in that: step 2) described in the massfraction of hydrochloric acid be 9% ~ 30%; The mass ratio of described hydrochloric acid and filter cake A is 8 ~ 11:1.
6. the recycling processing method of red mud according to claim 1, is characterized in that: the massfraction of hydrogen peroxide solution described in step 3) is 12% ~ 28%; The volume ratio of described hydrogen peroxide solution and liquor B is 0.10 ~ 0.30:100.
7. the recycling processing method of red mud according to claim 1, is characterized in that: the massfraction of phosphoric acid described in step 3) is 40% ~ 85%; The volume ratio of described phosphoric acid and liquor B is 2.0 ~ 20:100.
8. the recycling processing method of red mud according to claim 1, is characterized in that: regulate the method for reaction system pH to be in reaction system, add the sodium hydroxide solution that massfraction is 8% ~ 30% in step 3).
9. the recycling processing method of red mud according to claim 1, is characterized in that: the massfraction of sodium sulfide solution described in step 4) is 5% ~ 20%; Described in step 5) and step 7), the massfraction of caustic soda soln is 8% ~ 30%; The massfraction of ammoniacal liquor described in step 6) is 8% ~ 20%; The massfraction of hydrochloric acid described in step 8) is 9% ~ 30%.
10. the recycling processing method of red mud according to claim 1, is characterized in that: step 2) described in filter cake B for reclaiming titanium dioxide.
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| CN102826560A (en) * | 2012-08-29 | 2012-12-19 | 潘国雄 | Red mud resource utilization method |
| CN102897816A (en) * | 2012-09-29 | 2013-01-30 | 贵州绿水青山环保科技有限公司 | Deep recycling method of red mud |
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| CN102826560A (en) * | 2012-08-29 | 2012-12-19 | 潘国雄 | Red mud resource utilization method |
| CN102897816A (en) * | 2012-09-29 | 2013-01-30 | 贵州绿水青山环保科技有限公司 | Deep recycling method of red mud |
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