CN106517200A - Method for preparing metal carbonate - Google Patents
Method for preparing metal carbonate Download PDFInfo
- Publication number
- CN106517200A CN106517200A CN201510571961.2A CN201510571961A CN106517200A CN 106517200 A CN106517200 A CN 106517200A CN 201510571961 A CN201510571961 A CN 201510571961A CN 106517200 A CN106517200 A CN 106517200A
- Authority
- CN
- China
- Prior art keywords
- metal
- sulfate
- containing ammonium
- solution
- ammonium hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for preparing a metal carbonate. The method comprises use of a solution containing ammonium hydroxide and CO2 gas for precipitation reaction of a metal sulfate solution to obtain a metal carbonate and / or basic carbonate and precipitated wastewater; addition of a calcium-containing alkaline substance into the precipitated wastewater for recycling to obtain an alkaline solution containing ammonium hydroxide; and returning of the alkaline solution for cyclic utilization as the solution containing ammonium hydroxide. By use of the solution containing ammonium hydroxide and the CO2 gas for precipitation reaction of the metal sulfate solution, metal carbonate and / or basic carbonate with different physical properties can be obtained, and the precipitated wastewater can be converted into the solution containing ammonium hydroxide for reuse for metal carbonate preparation. The method combines metal smelting separation process and waste water treatment, a metal carbonate product is obtained, meanwhile, the ammonium sulfate wastewater is recycled, and the method has the advantages of short flow, low energy consumption, low cost, low carbon and greenness.
Description
Technical field
The present invention relates to metal smelt and industry environmental protection field, in particular to a kind of preparation method of metal carbonate.
Background technology
In metal smelt separation production process, various solution of metal sulfates generally prepare metal carbonate using ammonium bicarbonate precipitation,
A large amount of ammonium sulfate waste waters can be produced in preparation process, can produce a large amount of low-concentration sulfuric acid ammonium waste water particularly by washing process.
During metal sulfate prepares metal carbonate, the ammonia nitrogen class waste water of the liquid containing ammonium sulfate that ammonium bicarbonate precipitation operation is produced,
As containing foreign ions such as a large amount of Ca, Mg, Fe, Al, Si, waste component is complicated, and ammonia-nitrogen content is relatively low, processes phase
To difficulty, more difficult using the process of end conventional method, processing cost is high.
Have enterprise to replace the method for ammonium bicarbonate precipitation solving using sodium carbonate or sodium acid carbonate precipitation, but the method exist it is several
Problem：A the price of () carbon sodium is higher than carbon ammonium, increased production cost；B the molecular weight of () sodium is bigger than ammonia, total in the waste water of generation
Salt amount is higher than ammonium salt 1.23 times, i.e. the total release of pollutant is not reduced, and the problem caused into after underground water is more；(c)
The discharge standard of total salt amount in waste water is once put into effect in country or place, in addition it is also necessary to administer again.
In the research and application that the circulation and stress of industrial brine waste is processed, study at present it is more be using UF membrane concentration method,
Evaporative crystallization method, vaporizing extract process and break point chlorination etc..Membrane separation process be using the ion in selective penetrated property separation water, molecule or
Person's particulate, treatment effect preferably, but easily cause fouling membrane.Evaporative crystallisation process refers to that brine waste Jing is concentrated by evaporation, and reaches
Saturation state, makes salt form nucleus in waste water, progressively generates then crystalline solid and then realizes separating, and the method is applied to height
The process of salt waste water.Vaporizing extract process refers to and allows waste water and water vapour directly contact, the volatile materials in waste water is expanded by a certain percentage
It is scattered in gas phase, so as to reach the purpose for separating pollutant from waste water, is mainly used in the process of effumability pollutant.Folding
Point chloridising is that a certain amount of chlorine or sodium hypochlorite are added in waste water, makes ammonia nitrogen be oxidized to N2, so as to reach removal ammonia
The purpose of nitrogen.It is higher, tight to waste water quality requirement that these methods are respectively provided with one-time investment height, technological process length, operating cost
The shortcomings of lattice, high cost is recycled, with whole recyclings, calcic magnesium ion complicated to impure ion is higher for shipwreck
Ammonium sulfate waste water is less suitable for, thus application industrially is restricted.
The nineties in 20th century rises the ammonia nitrogen class waste water that a kind of chemical precipitation method processes such liquid containing ammonium sulfate.The method needs to add
Mg2+、PO4 3-And alkaline solution, by adjusting pH value, form double salt MgNH4PO4·6H2(MAP, long-acting slow-release are combined O
Fertilizer).To the clearance of ammonia nitrogen up to more than 95%, in the waste water after process, ammonia-nitrogen content is 20mg/L-40mg/L to the method.But
It is that the ammonia nitrogen removal frank of the method is affected by initial ammonia nitrogen concentration in waste water, it is adaptable to high-concentration sulfuric acid ammonium waste water.And locate
The alkalescent waste water of sulfur acid sodium is produced after reason, although is solved the problems, such as ammonia nitrogen, but is not solved discharged wastewater met the national standard and comprehensive profit
Question of substance.
For the process of dilute sulfuric acid ammonium waste water, the U.S. have document report using multistep evaporation, concentration method obtain sulphur ammonium solid and
Removing ammonia.Japan also has patent document to disclose to add excessive potassium hydroxide or potassium oxide toward waste water, make the sulfate radical in solution
Ion removes ammonia as most of potassium sulfate solids of sedimentation, re-evaporation.China has disclosure to do precipitating reagent removing ammonia therein using magnesium salts
Nitrogen, then adjust pH value condensing crystallizing.It is another to also have patent to disclose the method for reclaiming solid ammonium sulfate from dilute sulfuric acid ammonium, first blowing air
By Fe2+Oxide layer Fe3+Removing, then dihydrate gypsum and weak aqua ammonia being generated with lime treatment, weak aqua ammonia is adsorbed by ion exchange bed
Removing ammonia, is regenerated to resin with dilute sulfuric acid after ammonia saturation, and the dilute sulfuric acid ammonium liquefied ammonia neutralization for obtaining is true again to after pH value 8.0
Empty concentration and crystallization.The common drawback of the processing method of any of the above dilute sulfuric acid ammonium waste water is that handling process is complicated, and processing cost
It is high.
Therefore, in terms of the comprehensive reutilization of the liquid containing ammonium sulfate waste water for producing in metal carbonate preparation process, it is still necessary to existing
Technology is improved, and can be circulated the metal carbonate for utilizing with the waste water after providing a kind of cheap, environmental protection and processing and prepare
Technique.
The content of the invention
Present invention is primarily targeted at a kind of preparation method of metal carbonate is provided, to provide a kind of cheap, environmental protection and process
Waste water afterwards can be circulated the metal carbonate preparation technology for utilizing.
To achieve these goals, according to an aspect of the invention, there is provided a kind of preparation method of metal carbonate, the system
Preparation Method includes：Step S1, carries out precipitating anti-to solution of metal sulfates using the solution containing ammonium hydroxide and carbon dioxide
Should, obtain metal carbonate and/or basic metal carbonates and precipitation waste liquid；Step S2, adds calcic in precipitation waste liquid
Alkaline matter is recycled, and obtains the alkaline solution containing ammonium hydroxide；And step S3, by alkaline solution return to step S1
Utilization is circulated as the solution containing ammonium hydroxide.
Further, in step sl, control the pH value of precipitation reaction in the range of 2.0～10.0.
Further, step S1 includes：Step S11：Carbon dioxide is passed through in the solution containing ammonium hydroxide to be carbonized
Reaction, obtains the solution containing ammonium hydrogen carbonate；And step S12：Solution containing ammonium hydrogen carbonate is mixed with solution of metal sulfates,
Obtain metal carbonate and/or basic metal carbonates and precipitation waste liquid.
Further, step S1 includes：Step S11 '：Solution containing ammonium hydroxide is mixed with solution of metal sulfates,
Obtain metal alkaline slurries；And step S12 '：To in metal alkaline slurries being passed through carbon dioxide carries out carburizing reagent, obtains
To metal carbonate and/or basic metal carbonates and precipitation waste liquid.
Further, step S1 includes：By the solution containing ammonium hydroxide, solution of metal sulfates and carbon dioxide simultaneously
Mixing is reacted, and obtains metal carbonate and/or basic metal carbonates and precipitation waste liquid.
Further, step S11 includes：To in the solution containing ammonium hydroxide being passed through carbon dioxide carries out carburizing reagent, and
The pH value of control carbonation reaction in the range of 7.0～10.0, the slurries after being carbonized；And the slurries after carbonization are carried out
Separation of solid and liquid, obtains the solution containing ammonium hydrogen carbonate.
Further, in step s 2, the alkaline matter of calcic is with OH-Meter, OH-Molal quantity with precipitation waste liquid in NH4 +
Molal quantity ratio be 1.00～1.30:1.
Further, step S2 includes：Step S21, is adjusted the pH value for precipitating waste liquid to 3.0～6.0 with the alkaline matter of calcic,
Obtain solidliquid mixture；Step S22, filters to solidliquid mixture, obtains filtrate；And step S23, relay to filtrate
The continuous alkaline matter for adding calcic, obtains the solution containing ammonium hydroxide.
Further, the alkaline matter of calcic is one or more in calcium hydroxide, calcium oxide and light dolomite.
Further, metal sulfate include alkali metal sulfates, alkali earth metal sulfate, transition metal sulfate, gallium sulfate,
Any one in Ge(SO), STANNOUS SULPHATE CRYSTALLINE and antimony sulfate；It is preferred that transition metal sulfate includes sulfuric acid rare earth, zirconium sulfate, sulfuric acid
Any one in hafnium, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate.
Further, carbon dioxide is by the gas in metal carbonate technology of threonates, metal carbonate roasting kiln gas and pot
One or more recovery in kiln gas are obtained.
Further, in step S2, while the solution containing ammonium hydroxide is obtained, also obtain the solid slag of sulfur acid calcium；To containing
The solid slag of calcium sulfate carries out purifying and obtains calcium sulfate, and calcium sulfate is used as to prepare the raw material of gypsum or cement.
Using technical scheme, by using the solution containing ammonium hydroxide and carbon dioxide to solution of metal sulfates
Carry out precipitation reaction to prepare metal carbonate and/or basic metal carbonates, then the precipitation of the liquid containing ammonium sulfate solution to producing is given up
The alkaline matters such as the calcium hydroxide slurry (white lime) that liquid is obtained with calcium hydroxide, calcium oxide or lime slaking carry out alkali and turn
Recycling, obtains the alkaline solution containing ammonium hydroxide；Then using the alkaline solution containing ammonium hydroxide again as containing hydroxide
The solution of ammonium, with CO2Gas carries out precipitation reaction to solution of metal sulfates.The preparation method technological process is short, and waste water is controlled
Reason is combined with metal smelt separating technology, and energy consumption and the cost of raw material are low, is obtaining metal carbonate and/or basic metal carbonic acid
While product salt, ammonium sulfate waste water is recycled, and flow process is short, less energy consumption, low cost, green low-carbon.
Description of the drawings
The Figure of description for constituting the part of the application is used for providing a further understanding of the present invention, the schematic reality of the present invention
Apply example and its illustrate, for explaining the present invention, not constituting inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the preparation method schematic flow sheet of the middle metal carbonate according to a kind of preferred embodiment of the invention.
Specific embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can be mutually combined.
The present invention is described in detail below in conjunction with embodiment.
As background section is previously mentioned, the substantial amounts of waste water containing ammonia nitrogen is often produced during metal carbonate is prepared,
Or and method of wastewater treatment of the prior art exist process after waste water cannot qualified discharge, or complex treatment process, place
The problems such as reason high cost.In order to provide a kind of preparation technology of cheap, efficient and environmentally friendly metal carbonate, of the invention a kind of
In typical embodiment, there is provided a kind of preparation method of metal carbonate, as shown in figure 1, the preparation method includes：Step
Rapid S1, carries out precipitation reaction using the solution containing ammonium hydroxide and carbon dioxide to solution of metal sulfates, obtains metal carbon
Hydrochlorate and/or basic metal carbonates and precipitation waste liquid；Step S2, adds the alkaline matter of calcic to carry out back in precipitation waste liquid
Receipts process, obtains the alkaline solution containing ammonium hydroxide, and step S3, using alkaline solution return to step S1 as containing ammonium hydroxide
Solution be circulated utilization.
The above-mentioned preparation method of the present invention, by using the solution containing ammonium hydroxide and carbon dioxide to solution of metal sulfates
Carry out precipitation reaction to prepare metal carbonate and/or basic metal carbonates, then the precipitation of the liquid containing ammonium sulfate solution to producing is given up
The alkaline matters such as the calcium hydroxide slurry (white lime) that liquid is obtained with calcium hydroxide, calcium oxide or lime slaking carry out alkali and turn
Recycling, obtains the alkaline solution containing ammonium hydroxide；Then by alkaline solution return to step S1 containing ammonium hydroxide, again
As the solution containing ammonium hydroxide, with CO2Gas carries out precipitation reaction to solution of metal sulfates.The preparation method technological process
It is short, waste water treatment is combined with metal smelt separating technology, energy consumption and the cost of raw material are low, obtain metal carbonate and/or
While basic metal carbonates product, effective process nitrogen-containing wastewater is gone back, recycling for ammonia nitrogen waste water is realized.
And, the above-mentioned preparation method of the present invention, when the calcium hydroxide obtained with calcium hydroxide, calcium oxide or lime slaking
When the alkaline matter of the calcics such as slurry (white lime) carries out alkali turn recycling to the precipitation waste liquid of liquid containing ammonium sulfate, obtaining hydrogeneous
While the alkaline solution of amine-oxides, additionally it is possible to obtain the solid slag of sulfur acid calcium, as shown in figure 1, carrying out acid to the solid slag
The purification measures such as change, washing can obtain calcium sulfate, and calcium sulfate can act as preparing the raw material of gypsum or cement.Additionally, the preparation
Carbon dioxide in method, can recycle the CO that metal production process or boiler are produced2Gas, not only realizes
Application in metal carbonate preparation, and reduce greenhouse gas emission.
In above-mentioned steps S1, according to the difference of the be intended to metal sulfate species for precipitating, solution and two of the control containing ammonium hydroxide
The amount of carbon oxide gas so that the pH value of precipitation reaction is in suitable scope.In a kind of preferred embodiment of the invention, control
The pH value of precipitation reaction processed is in the range of 2.0～10.0.PH value control can be covered into a variety of metals within the above range
Sulfate liquor obtains condition when respective metal carbonate and/or basic metal carbonates.
In the above-mentioned preparation method of the present invention, step S1 is to prepare metal carbonate and/or basic metal carbonic acid by metal sulfate
The step of salt, cause metal sulfate that precipitation reaction occurs so as to obtain gold using the solution containing ammonium hydroxide and carbon dioxide
Category carbonate and/or basic metal carbonates.Thus, in this step, carry out being mixed with any kind of mode between three
The step of metal carbonate for arriving and/or basic metal carbonates, is applied to the present invention.In a kind of preferred embodiment of the invention,
Above-mentioned steps S1 include：Step S11：To in the solution containing ammonium hydroxide being passed through carbon dioxide carries out carburizing reagent, obtains
Solution containing ammonium hydrogen carbonate；And step S12：Solution containing ammonium hydrogen carbonate is mixed with solution of metal sulfates, metal carbon is obtained
Hydrochlorate and/or basic metal carbonates and precipitation waste liquid.
The concrete reaction equation of above-mentioned steps S11 is as follows：
NH4OH+CO2→NH4HCO3
The concrete reaction equation of above-mentioned steps S12 is as follows：
A(SO4)x/2+x NH4HCO3→A(CO3)x/2↓+x/2CO2↑+x/2(NH4)2SO4+x/2H2O；Or be
2A(SO4)x/2+2x NH4HCO3→A2(OH)x(CO3)x/2↓+3x/2CO2↑+x(NH4)2SO4+x/2H2O
Wherein, A is metal cation.
Above preferred embodiment is that the solution containing ammonium hydroxide and carbon dioxide are initially formed ammonium hydrogen carbonate, then with bicarbonate
Ammonium makes metal sulphate precipitation as precipitating reagent, so as to obtain metal carbonate and/or basic metal carbonates.Entered using which
The preparation of row metal carbonate and/or basic metal carbonates, using carbonizatin method prepare i.e. ammonium hydrogen carbonate activity it is higher, use
Make to make precipitation reaction rapider during precipitating reagent precipitation metal sulfate.And, can be synthesized by controlling being passed through for carbon dioxide
Compound precipitantses, synthesized compound precipitantses proportioning are different, then the precipitation particle for preparing is constituted, structure is variant.Also may be used
So that the solution containing ammonium hydroxide and the ammonium bicarbonate soln of carbon dioxide are deposited standby, or further prepared by evaporative crystallization
The storage of ammonium hydrogen carbonate solid product is standby.
In another kind preferred embodiment of the invention, above-mentioned steps S1 include：Step S11 '：By containing ammonium hydroxide solution with
Solution of metal sulfates is mixed, and obtains metal alkaline solution；And step S12 '：Dioxy is passed through in metal alkaline solution
Changing carbon gas carries out carburizing reagent, obtains metal carbonate and/or basic metal carbonates and precipitation waste liquid.
Above-mentioned steps S11 ' concrete reaction equation it is as follows：
y NH4OH+B(SO4)y/2→B(OH)y+y/2(NH4)2SO4
Above-mentioned steps S12 ' concrete reaction equation it is as follows：
B(OH)y+y/2CO2→B(CO3)y/2+y/2H2O；Or be
2B(OH)y+y/2CO2→B2(OH)y(CO3)y/2+y/2H2O
Wherein, B is metal cation.
After the preferred embodiment is by first being mixed the solution containing ammonium hydroxide with solution of metal sulfates, metal alkaline is obtained
Solution；Then being passed through carbon dioxide in metal alkaline solution again carries out carburizing reagent, obtains metal carbonate and/or metal
Subcarbonate and precipitation waste liquid.In the preferred embodiment, obtain metal carbonate and/or basic metal carbonates be by using
The carbon dioxide carbonization of gas form is formed, and gaseous carbon dioxide compares the carbanion of liquid, contributes to by control
The flow velocity of the carbon dioxide being passed through and total flow are reaching the purpose of the metal carbonate for producing different structure and form.That is,
Be conducive to enterprise according to the be intended to product category for preparing and the difference of structure, can by metal sulfate be prepared into metal carbonate,
The salt that basic metal carbonates or both mix in varing proportions such that it is able to adapt to market to the diversified need of carbonate products
Ask.
In another preferred embodiment of the invention, above-mentioned steps S1 include：By the solution containing ammonium hydroxide, metal sulfate
Mixing is reacted simultaneously for solution and carbon dioxide, obtains metal carbonate and/or basic metal carbonates and precipitation is useless
Liquid.Solution containing ammonium hydrogen carbonate, solution of metal sulfates and carbon dioxide are mixed by the preferred embodiment simultaneously, are passed through
Control three's hybrid mode, autotelic can obtain metal carbonate of different nature and/or basic metal carbonates.Three's is mixed
Conjunction mode can be：1. the solution containing ammonium hydroxide and carbon dioxide are passed through in metal salt solution；2. three with three strands simultaneously
The mode of stream is added in the liquid of bottom.3. tower reactor is adopted, carbon dioxide is with metal salt solution and containing the molten of ammonium hydroxide
Liquid is fed from diverse location, and gas-liquid two-phase is mixed in a counter-current configuration.No matter with which kind of hybrid mode, mass flow is can
Adjust, by the control to flow and precipitation process, can obtain with ultra-fine, epigranular, pattern rule (such as class ball
Shape etc.), the metal carbonate/basic metal carbonates of the property such as good dispersion.
The concrete reaction equation of above-mentioned steps is as follows：
D(SO4)z/2+z NH4OH+z/2CO2→D(CO3)z/2+z/2(NH4)2SO4+z/2H2O；Or be
2D(SO4)z/2+2z NH4OH+z/2CO2→D2(OH)z(CO3)z/2+z(NH4)2SO4+z/2H2O；
Wherein, Dz+For metal cation.
It is initially formed containing ammonium bicarbonate soln above-mentioned, recycles ammonium bicarbonate soln to precipitate to metal sulfate as precipitating reagent
In the preferred embodiment of reaction, the solution containing ammonium hydrogen carbonate formed in step S11 is fully able to for entering to metal sulfate
Row precipitation reaction.In order to further improve the metal carbonate that obtains and/or basic metal carbonates after the efficiency and precipitation of precipitation
Purity, in another kind preferred embodiment of the invention, above-mentioned steps S11 include：It is passed through in the solution containing ammonium hydroxide
Carbon dioxide carries out carburizing reagent, and controls the pH value of carbonation reaction in the range of 7.0～10.0, after being carbonized
Slurries；And separation of solid and liquid is carried out to the slurries after carbonization, obtain the solution containing ammonium hydrogen carbonate.
As in the preparation method of the present invention, the solution containing ammonium hydroxide is circulated and utilizes, in order that formed containing carbonic acid
The solution of hydrogen ammonium is purer, and above preferred embodiment is by first being adjusted pH in the range of 7.0～10.0 with carbon dioxide so that contain
The micro calcium sulfate that may contain in the solution of ammonium hydroxide is converted to precipitation of calcium carbonate and is removed, higher so as to obtain purity
Solution containing ammonium hydrogen carbonate, further precipitates and obtains the higher metal carbonate of purity and/or basic metal carbonates.
In the above-mentioned preparation method of the present invention, with the alkaline matter of calcic to precipitating the step of waste liquid is recycled in, no
Only taken into full account the reasonable utilization to precipitating waste liquid this ammonia nitrogen waste water, and produce after also contemplating recycling it is possible
The process of waste residue.In order that utilization can be circulated after the recovered process of precipitation waste liquid, and discharge waste has fewer environmental impacts,
In another preferred embodiment of the invention, in above-mentioned steps S2, the alkaline matter of calcic is with OH-Meter, OH-Molal quantity with
NH in waste water4 +Molal quantity ratio be 1.00～1.30:1.Wherein, with OH-Meter, refers to the alkaline matter of calcic with its hydrogen
The OH that the form calculus of oxide can be provided-。
Concrete reaction equation is as follows：
wNH4 ++M(OH)w→wNH4OH+Mw+；Or,
2wNH4 ++M2Ox+x H2O→2wNH4OH+2Mw+；
Wherein, M (OH)w/M2OwFor alkaline matter.
In above preferred embodiment, control, in above-mentioned suitable scope, both to make by the amount of the alkaline matter of the calcic that will be added
Ammonium ion be enough to be completely converted into ammoniacal liquor, avoid base excess to cause solid slag and filtrate alkalescence bigger than normal again.Solid slag alkalescence is bigger than normal
When, direct press filtration is stacked can not only make alkalization of soils, and harmful components therein (particularly alkali composition) is drenched through weathering
Filter, the invasion polluted-water of rainwash and soil；When filtrate alkalescence is bigger than normal, directly discharge can cause larger harm to water body,
The destruction ecological balance.Which is carried out when in-depth is processed, equipment to be caused larger corrosivity again, and more acidic chemicals need to be consumed
Raw material is reducing alkalescence.
Above-mentioned steps S2 of the present invention are, to step S1 while metal carbonate and/or basic metal carbonates is obtained, to produce
The precipitation waste liquid of liquid containing ammonium sulfate the step of recycled, thus, the alkaline matter of any utilization calcic just precipitates waste liquid
In ammonium ion be converted to the operation of the solution containing ammonium hydroxide (i.e. ammoniacal liquor) and be applied to the present invention.The present invention another
In preferred embodiment, above-mentioned steps S2 include：S21, with the alkaline matter of calcic by the pH value for precipitating waste liquid adjust to
3.0～5.0, obtain solidliquid mixture；Step S22, filters to solidliquid mixture, obtains filtrate；And step S23, to
The alkaline matter of calcic is continuously added in filtrate, obtains the solution containing ammonium hydroxide.
Above preferred embodiment, by first with the alkaline matter of calcic by the pH value of the precipitation waste liquid containing ammonium sulfate adjust to
3.0～5.0, contributing to for the beavy metal impurity ion such as Fe, Al, Zn, the Cu that may contain in precipitation waste liquid being initially formed precipitation is carried out
Effectively remove.The alkaline matter for continuously adding calcic in the filtrate obtained to after removing the heavy metal precipitations such as Fe, Al, Zn, Cu enters
Row pH value is adjusted so that in precipitation waste liquid, the calcium ion that may contain and sulfate ion combine to form calcium sulfate precipitation and further
Be removed, the solution containing ammonium hydroxide higher so as to obtain purity, so precipitation obtain the higher metal carbonate of purity and/or
Basic metal carbonates.The recycling step, the not only complicated ammonia nitrogen waste water of effective process, and realize the closed circuit of ammonia
Recycle, and the consumption of the precipitating reagents such as ammonia is greatly reduced, and can realize that the safety dumping of possible solid slag is processed.
Carry out during recycling obtained containing Ammonia, vapour can also being passed through in the alkaline matter of above-mentioned addition calcic
Carry preparing ammonia, or the alkaline solution containing ammonium hydroxide for finally giving is carried out into stripping and prepare ammonia.The ammonia that collection is recovered to
Gas, and which is together prepared into metal carbonate or metal for carrying out precipitation reaction to solution of metal sulfates with carbon dioxide
In the processing step of subcarbonate, the higher metal carbonate of purity or basic metal carbonates can be obtained.
In the above-mentioned preparation method of the present invention, the alkaline matter one side of calcic turns for precipitating the ammonium ion alkali in waste liquid
For ammoniacal liquor；On the other hand for being precipitated to form calcium sulphate solid slag to precipitating the sulfate ion in waste liquid.Thus, on
The alkaline matter for stating calcic in embodiment include but are not limited in calcium hydroxide, calcium oxide, light dolomite one or more.
The alkaline matter of above-mentioned several calcics has the advantages that cost is relatively low, wide material sources.
The above-mentioned preparation method of the present invention, the metal sulfate for being used include but are not limited to alkali metal sulfates, alkaline-earth metal
Any one in sulfate, transition metal sulfate, gallium sulfate, Ge(SO), STANNOUS SULPHATE CRYSTALLINE and antimony sulfate；It is preferred that transition metal
Sulfate includes any one in sulfuric acid rare earth, zirconium sulfate, hafnium sulfate, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate.
Above-mentioned metal sulfate is prepared into carbonate by using the preparation method of the present invention, not only will be above-mentioned pure or unpurified
Metal sulfate is converted to the higher metal carbonate of purity and using value and/or basic metal carbonates, and to preparation process
The nitrogen-containing wastewater of middle generation has carried out reasonable utilization, and while ammonia closed cycle is realized, the solid slag to being likely to occur is also real
Effective process is showed.Such as in above-mentioned preparation process S2, while the solution containing ammonium hydroxide is obtained, sulfur acid is also obtained
The solid slag of calcium；Purifying is carried out to the solid slag of sulfur acid calcium and obtains calcium sulfate, the calcium sulfate can serve as preparing the original of gypsum or cement
Material.
In the above-mentioned preparation method of the present invention, the source of carbon dioxide can be various, either reclaim from industrial waste gas
The carbon dioxide for obtaining, or industrially all fitted by the carbon dioxide of technical grade pure obtained in other reactions
For the present invention.Consider that the carbon dioxide of the present invention preferably produces work by metal carbonate from environmental protection and reducing energy consumption angle
One or more recovery in gas, metal carbonate roasting kiln gas and boiler smoke in skill are obtained.From above-mentioned several techniques
During the gas that produces be raw material, obtain carbon dioxide after compression, purification or other process steps, both to above-mentioned
Process gas have carried out reasonable utilization, and low-carbon emission reduction meets environmental requirement；And and realize effective application of carbon dioxide.
Angle is utilized from the Efficient Cycle of cost of material, energy consumption so that the above-mentioned preparation method of the present invention becomes the height that enterprise is really suitable for
Effect and the metal carbonate salt production process of low energy consumption.
Below in conjunction with specific embodiments further illustrating beneficial effects of the present invention.
Using icp mses, inductive coupling plasma emission spectrograph and atomic absorption spectrophotometer pair
The constant and trace element of product is measured, and the granularity of product is measured using laser particle analyzer.
Embodiment 1
By lanthanum sulfate cerium solution 10L (concentration is 15g/L, in terms of REO) of rare earth extraction separating-purifying with it is molten containing ammonium hydroxide
Liquid is added in precipitation reactor, while industrial carbon dioxide gas is passed through in precipitation reactor, pH value in control course of reaction
It is maintained between 6.5～7.0 scopes, reaction continues to obtain lanthanum carbonate cerium slurry after 3h terminates, and is filtered, washed and is dried
To 332.0g artificial lanthanite cerium crystals (REO is 45wt%), the REO rate of recovery is 99.6%；The waste liquid being filtrated to get simultaneously,
The as waste water of liquid containing ammonium sulfate.
Calcium oxide is added in the waste water of liquid containing ammonium sulfate, the mole of calcium oxide is made (with OH-Meter) with ammonium sulfate waste water in ammonium root from
The mole ratio of son is n (OH-):n(NH4 +)=1.08:1, ammonia radical ion is 99.0% to ammoniacal liquor conversion ratio.Separation of solid and liquid obtains hydrogeneous
The solid slag of ammonium hydroxide solution and sulfur acid calcium.
Alkaline solution containing ammonium hydroxide is recycled.The solid slag of sulfur acid calcium obtains calcium sulfate product by purification process.
Embodiment 2
By the samarium sulphate solution (concentration is 20g/L, in terms of REO) of rare earth extraction separating-purifying with the solution containing ammonium hydroxide from tower
Formula reactor top is passed through, and the flow of samarium sulphate solution is 5m3/h；Carbon dioxide is passed through from tower reactor bottom simultaneously,
Gas-liquid counter current is formed, and pH is maintained between 6.5～7.0 scopes in controlling course of reaction, obtains samaric carbonate slurry, enter after reaction
Row filter, washing and drying obtain be hydrated samaric carbonate crystal, yield be 181.3kg/h (REO is 55wt%), the rate of recovery of samarium
For 99.7%；Precipitation waste liquid, the as waste water of liquid containing ammonium sulfate is reclaimed after filtering simultaneously, is carried out process recovery by embodiment 11 and is obtained
Solution reuse containing ammonium hydroxide.
Carbon dioxide reclaims what is obtained for the gas and samaric carbonate roasting kiln gas in samarium sulphate production technology.
It is thinner that Jing tests the samaric carbonate crystal size, between 1～3 μm.
Embodiment 3
By rare earth extraction isolated sulfuric acid mixed rare earth solution 10m3(concentration is 25g/L, in terms of REO) and contain hydroxide
The solution of ammonium is added in precipitation reaction kettle, while carbon dioxide is passed through in precipitation reaction kettle, pH in control course of reaction
It is maintained between 6.8～7.0 scopes, reaction continues to obtain mixed rare earth carbonate slurry after 4h terminates, and is filtered, washed and is got rid of
Dry to obtain 497.5kg hydrations mixed rare earth carbonate crystal (REO is 50wt%), rare earth yield is 99.5%, while after filtering
Precipitation waste liquid, the as waste water of liquid containing ammonium sulfate is reclaimed, and process recovery is carried out by embodiment 12 and is obtained the solution reuse containing ammonium hydroxide.
Carbon dioxide reclaims what is obtained for the gas and mixed rare earth carbonate roasting kiln gas in rare-earth smelting separating and producing.
Embodiment 4
First the cerous sulfate 10L (concentration is 18g/L, in terms of REO) by purity for 99.99wt% is added with the solution containing ammonium hydroxide
Enter in precipitation reactor, while being passed through carbon dioxide in precipitation reactor, in control course of reaction, pH is maintained at
Between 6.2～7.0 scopes, reaction continues to obtain cerous carbonate slurry after 4h terminates, and carries out filtering, repeatedly washing and drying obtain 344.8g
Cerium carbonate hydrate crystal (REO is 52wt%), the rate of recovery of cerium is 99.6%；Precipitation waste liquid is reclaimed after filtering simultaneously, is as contained
The waste water of ammonium sulfate, carries out process recovery by embodiment 13 and obtains the solution reuse containing ammonium hydroxide.
It is few due to reclaiming the impurity content such as Fe, Si in the solution containing ammonium hydroxide for obtaining, and the cerous carbonate crystal formation for being formed is good, leads to
Cross repeatedly washing purity can be obtained for 99.99wt% carbonic acid cerium crystals.
Comparative example 1
Ammonium hydrogencarbonate is added into precipitation carbonic acid in cerous sulfate 10L (concentration is 18g/L, in terms of REO) of the purity for 99.99wt%
Cerium, between control reaction pH=6.2～7.0 scope；Jing separation of solid and liquid, obtains cerous carbonate and liquid containing ammonium sulfate that purity is 99.95wt%
Waste water.
As ammonium hydrogen carbonate has brought the impurity such as Fe, Si, Al into, cerous carbonate purity is have impact on.
Embodiment 5
First by the cerous sulfate solution 10L (concentration is 15g/L, in terms of REO) of rare earth extraction separating-purifying with it is molten containing ammonium hydroxide
Liquid is reacted in being added to precipitation reactor, then is passed through carbon dioxide in precipitation reactor, controls pH during W-response
It is maintained between 6.2～7.0 scopes, temperature is maintained between 50 DEG C～60 DEG C, reaction continues to obtain cerous carbonate slurry after 4h terminates,
Carry out filtering, wash and drying obtains 287.3g carbonic acid cerium crystals (REO is 52wt%), the rate of recovery of cerium is 99.6%；Jing is surveyed
Examination, the cerous carbonate crystal size are larger, between 15～25 μm.Recovery precipitation waste liquid after filtering simultaneously, as liquid containing ammonium sulfate
Waste water, carries out process recovery by embodiment 13 and obtains the solution reuse containing ammonium hydroxide.
Wherein, because the solution containing ammonium hydroxide is to add calcium oxide to enter the waste water of liquid containing ammonium sulfate using the method shown in embodiment 13
Row is processed and reclaims what is obtained, and exothermic heat of reaction makes the solution temperature containing ammonium hydroxide for preparing have uniform temperature, is precipitated
The energy of external heat can be reduced during reaction.
Embodiment 6
Take zirconyl chloride solution 10L (concentration is 100g/L) to be added in precipitation reactor, be passed through ammoniacal liquor in precipitation reactor extremely
System pH reaches 2.0～2.8, is then passed through the solution containing ammonium hydroxide and technical grade carbon dioxide gas in precipitation reactor simultaneously
Body is reacted；In course of reaction reaction system be open normal pressure, carburizing reagent continue 3h terminate after obtain zirconium carbonate slurry, enter
Row is filtered, washing and drying obtain zirconium carbonate, and the rate of recovery of zirconium is 99.5% (in terms of zirconium oxide)；Reclaim after filtering simultaneously and filter
Waste liquid, as ammonium sulfate waste water, carry out process recovery by embodiment 13 and obtain the solution reuse containing ammonium hydroxide.
Embodiment 7
First by the cobalt sulfate solution 10L (concentration is 50g/L, in terms of REO) of rare earth extraction separating-purifying with it is molten containing ammonium hydroxide
Liquid is reacted in being added to precipitation reactor, then is passed through carbon dioxide in precipitation reactor, controls pH during W-response
Be maintained between 9.5～10.0 scopes, reaction continues cobalt carbonate slurry to be obtained after 6h terminates, carry out filtering, wash and drying is obtained
Cobalt carbonate crystal, the rate of recovery of cobalt is 99.5% (in terms of cobalt oxide)；Precipitation waste liquid, as liquid containing ammonium sulfate is reclaimed after filtering simultaneously
Waste water, by embodiment 13 carry out process reclaim obtain the solution reuse containing ammonium hydroxide.
Embodiment 8
Carbon dioxide is passed through in Ammonia, pH=9.5～10.0 in carbonation reaction, are controlled to, the slurry that will be formed
Liquid is filtrated to get the composite precipitation agent solution containing ammonium hydrogen carbonate.By which, (concentration is 35g/L, with nickel oxide with nickel sulfate solution 10L
Meter) reaction in precipitation reactor is added to, pH=8.2～10.0 are controlled in course of reaction, reaction temperature is controlled in 45～50 DEG C of scopes
It is interior；Jing separation of solid and liquid, obtains 581.0g basic nickel carbonates (NiO is 60wt%), and the rate of recovery of nickel is 99.6%；Filter simultaneously
Precipitation waste liquid, the as waste water of liquid containing ammonium sulfate is reclaimed afterwards, is carried out process recovery by embodiment 14 and is obtained the solution containing ammonium hydroxide time
With.
Wherein, because the solution containing ammonium hydroxide is to add calcium oxide to carry out process recovery to the waste water of liquid containing ammonium sulfate to obtain, exothermic heat of reaction
Make the solution temperature containing ammonium hydroxide for preparing that there is uniform temperature, need not external heat when carrying out precipitation reaction.
Embodiment 9
Industrial carbon dioxide gas is passed through in Ammonia, pH=7.0～8.0 in carbonation reaction, are controlled to, by what is formed
Slurries are filtrated to get the composite precipitation agent solution containing ammonium hydrogen carbonate.By which, (concentration is 20g/L, to aoxidize with praseodymium sulfate solution 10L
Nickel meter) reaction in precipitation reactor is added to, pH=6.2～6.8 are controlled in course of reaction；Jing is filtered, and obtains 398.8g praseodymium carbonates,
The rate of recovery of praseodymium is 99.7%；Reclaim after filtering simultaneously and precipitate waste liquid, as the waste water of liquid containing ammonium sulfate, at embodiment 14
Reason is reclaimed and obtains the solution reuse containing ammonium hydroxide.
Embodiment 10～17 is the specific embodiment of waste water recycling device
The waste water of the liquid containing ammonium sulfate that embodiment 10～17 is produced with metal carbonate and/or basic metal carbonates preparation process is as original
Material, adds the alkaline matter of calcic, on the basis of the mole of ammonium ion in ammonium sulfate waste water, is proportionally added into the alkali of calcic
Ammonium ion is converted into ammonium hydroxide by property material, and separation of solid and liquid obtains consolidating for the alkaline solution containing ammonium hydroxide and sulfur acid calcium
Body slag；
Alkaline solution containing ammonium hydroxide proceeds to recycle；
The solid slag of sulfur acid calcium obtains calcium sulfate product by purification process.
Concrete recycling situation is as shown in table 1：
Table 1：
The step of waste water recycling device in embodiment 18～20, is as follows.
Waste water with the liquid containing ammonium sulfate of embodiment 6 adjusts the pH value of the waste water of liquid containing ammonium sulfate as raw material with the alkaline matter of calcic,
Separation of solid and liquid is carried out, the element such as Fe, Al, heavy metal ion in removing waste liquid.Continue to add oxygen in the waste water of containing ammonium chloride
Change calcium.On the basis of the mole of ammonium ion in ammonium sulfate waste water, the alkaline matter of calcic is proportionally added into, by ammonium ion
It is converted into ammonium hydroxide.Separation of solid and liquid obtains the solid slag of the alkaline solution containing ammonium hydroxide and sulfur acid calcium.
Alkaline solution containing ammonium hydroxide continues to be circulated utilization using the step in embodiment 6.
The solid slag of sulfur acid calcium obtains calcium sulfate product by purification process.
The concrete response situation of embodiment 18～20 is as shown in table 2 below：
Table 2：
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
(1) solution of metal sulfates is carried out precipitation reaction to prepare by using the solution containing ammonium hydroxide and carbon dioxide
Metal carbonate and/or basic metal carbonates, then the precipitation waste liquid calcium hydroxide of the liquid containing ammonium sulfate solution to producing, oxidation
The alkaline matters such as the calcium hydroxide slurry (white lime) that calcium or lime slaking are obtained carry out alkali and turn recycling, obtain hydrogeneous
The alkaline solution of amine-oxides；Then using the alkaline solution containing ammonium hydroxide again as the solution containing ammonium hydroxide, with CO2Gas
Body carries out precipitation reaction to solution of metal sulfates.The preparation method technological process is short, and waste water treatment is separated work with metal smelt
Skill combines, and energy consumption and the cost of raw material are low, while metal carbonate and/or basic metal carbonates product is obtained, also
Effect has processed nitrogen-containing wastewater, realizes recycling for ammonia nitrogen waste water.
(2) calcium hydroxide slurry that above-mentioned preparation method of the invention can be obtained with calcium hydroxide, calcium oxide or lime slaking
The alkaline matter of the material calcic of with low cost, wide material sources such as (white lime), carries out alkali to the precipitation waste liquid of liquid containing ammonium sulfate and goes back to
Receipts process, while the alkaline solution containing ammonium hydroxide is obtained, additionally it is possible to obtain the solid slag of sulfur acid calcium, to the solid slag
Carry out purifying and can obtain calcium sulfate, and calcium sulfate can act as preparing the raw material of gypsum or cement.Additionally, in the preparation method two
Carbon oxide gas, can recycle the CO that metal production process or boiler are produced2Gas, not only realizes in metal carbonate
Application in preparation, and reduce greenhouse gas emission.
(3) technique is not high to the component requirements of liquid containing ammonium sulfate waste water, can process impure ion complicated, calcic magnesium ion
Waste water.
(4) during being adjusted containing the pH value of precipitation waste liquid with the alkaline matter of calcic, can by the foreign metal in waste water from
The son such as beavy metal impurity such as Fe, Al, Cu, Zn ion conversion is removed for precipitation Jing separation of solid and liquid, can be obtained by subsequent treatment
Purer calcium sulfate product, it is stable in properties, on environment without impact, can be used for the preparation of cement and other construction materials.
(5) pass through the recovery process waste gas (waste gas, metal carbonate roasting kiln gas and boiler in metal carbonate technology of threonates
Flue gas) in CO2Gas is carbonized, and is reduced greenhouse gas emission, is realized low-carbon emission.
As can be seen here, the preparation method of metal carbonate of the invention had both realized the variation preparation of metal carbonate, Er Qieshi
The comprehensive recycling of waste water in technical process is showed, the near-zero release of industrial wastewater, waste gas and/or waste can have been realized again, entirely
Process route resource utilization is high, and economic benefit and social benefit are all fairly obvious.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for those skilled in the art
For, the present invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made, etc.
With replacement, improvement etc., should be included within the scope of the present invention.
Claims (12)
1. a kind of preparation method of metal carbonate, it is characterised in that the preparation method includes：
Step S1, carries out precipitation reaction using the solution containing ammonium hydroxide and carbon dioxide to solution of metal sulfates,
Obtain metal carbonate and/or basic metal carbonates and precipitation waste liquid；
Step S2, in the precipitation waste liquid adds the alkaline matter of calcic to be recycled, obtains containing ammonium hydroxide
Alkaline solution；And
The alkaline solution is returned step S1 and is circulated profit as the solution containing ammonium hydroxide by step S3
With.
2. preparation method according to claim 1, it is characterised in that in step S1, controls the precipitation reaction
PH value is in the range of 2.0～10.0.
3. preparation method according to claim 1, it is characterised in that step S1 includes：
Step S11：To in the solution containing ammonium hydroxide being passed through carbon dioxide carries out carburizing reagent, obtains containing carbonic acid
The solution of hydrogen ammonium；And
Step S12：The solution containing ammonium hydrogen carbonate is mixed with the solution of metal sulfates, the metal carbonate is obtained
Salt and/or basic metal carbonates and the precipitation waste liquid.
4. preparation method according to claim 1, it is characterised in that step S1 includes：
Step S11 '：The solution containing ammonium hydroxide is mixed with the solution of metal sulfates, metal base is obtained
Property slurries；And
Step S12 '：To in the metal alkaline slurries being passed through carbon dioxide carries out carburizing reagent, obtains the metal
Carbonate and/or basic metal carbonates and the precipitation waste liquid.
5. preparation method according to claim 1, it is characterised in that step S1 includes：By described containing ammonium hydroxide
Solution, the solution of metal sulfates and carbon dioxide simultaneously mix and are reacted, obtain the metal carbonate and
/ or basic metal carbonates and the precipitation waste liquid.
6. preparation method according to claim 3, it is characterised in that step S11 includes：
Being passed through carbon dioxide in the solution containing ammonium hydroxide carries out carburizing reagent, and controls the carburizing reagent
The pH value of process in the range of 7.0～10.0, the slurries after being carbonized；And
Separation of solid and liquid is carried out to the slurries after the carbonization, the solution containing ammonium hydrogen carbonate is obtained.
7. preparation method according to claim 1, it is characterised in that in step S2, the alkaline matter of the calcic
With OH-Meter, the OH-Molal quantity and it is described precipitation waste liquid in NH4 +Molal quantity ratio be 1.00～1.30:1.
8. preparation method according to any one of claim 1 to 7, it is characterised in that step S2 includes：
Step S21, is adjusted the pH value of the precipitation waste liquid to 3.0～6.0 with the alkaline matter of the calcic, obtains solid-liquid
Mixture；
Step S22, filters to the solidliquid mixture, obtains filtrate；And
Step S23, continuously adds the alkaline matter of the calcic in the filtrate, obtains the solution containing ammonium hydroxide.
9. preparation method according to any one of claim 1 to 7, it is characterised in that the alkaline matter of the calcic is hydrogen
One or more in calcium oxide, calcium oxide and light dolomite.
10. preparation method according to claim 1, it is characterised in that the metal sulfate includes alkali metal sulfates, alkaline earth
Any one in metal sulfate, transition metal sulfate, gallium sulfate, Ge(SO), STANNOUS SULPHATE CRYSTALLINE and antimony sulfate；It is preferred that institute
Stating transition metal sulfate includes sulfuric acid rare earth, zirconium sulfate, hafnium sulfate, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate
In any one.
11. preparation methods according to claim 1, it is characterised in that the carbon dioxide is by metal carbonate technology of threonates
In gas, one or more recovery in metal carbonate roasting kiln gas and boiler smoke obtain.
12. preparation methods according to claim 1, it is characterised in that in step S2, are obtaining described containing ammonium hydroxide
Solution while, also obtain the solid slag of sulfur acid calcium；Purifying is carried out to the solid slag of the sulfur acid calcium and obtains calcium sulfate, institute
State calcium sulfate to be used as to prepare the raw material of gypsum or cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510571961.2A CN106517200B (en) | 2015-09-09 | 2015-09-09 | The preparation method of metal carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510571961.2A CN106517200B (en) | 2015-09-09 | 2015-09-09 | The preparation method of metal carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106517200A true CN106517200A (en) | 2017-03-22 |
| CN106517200B CN106517200B (en) | 2019-01-01 |
Family
ID=58345795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510571961.2A Active CN106517200B (en) | 2015-09-09 | 2015-09-09 | The preparation method of metal carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106517200B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115814751A (en) * | 2022-12-15 | 2023-03-21 | 贵州大学 | Method for preparing porous calcium silicate adsorbent by alkali-activated electrolytic manganese slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392332A (en) * | 2008-11-07 | 2009-03-25 | 北京科技大学 | Cleaning production technique for directly transforming rare earth sulfate bake ore to extract rare earth |
| CN101798627A (en) * | 2009-02-09 | 2010-08-11 | 有研稀土新材料股份有限公司 | Method for precipitating rare earth |
| CN102816930A (en) * | 2012-08-13 | 2012-12-12 | 南昌大学 | Method for gas phase precipitation of rare earth |
| CN103351017A (en) * | 2013-07-01 | 2013-10-16 | 南昌大学 | Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof |
| CN104117682A (en) * | 2013-04-27 | 2014-10-29 | 北京有色金属研究总院 | Method for preparing narrow range rare earth oxide with controllable particle size |
-
2015
- 2015-09-09 CN CN201510571961.2A patent/CN106517200B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392332A (en) * | 2008-11-07 | 2009-03-25 | 北京科技大学 | Cleaning production technique for directly transforming rare earth sulfate bake ore to extract rare earth |
| CN101798627A (en) * | 2009-02-09 | 2010-08-11 | 有研稀土新材料股份有限公司 | Method for precipitating rare earth |
| CN102816930A (en) * | 2012-08-13 | 2012-12-12 | 南昌大学 | Method for gas phase precipitation of rare earth |
| CN104117682A (en) * | 2013-04-27 | 2014-10-29 | 北京有色金属研究总院 | Method for preparing narrow range rare earth oxide with controllable particle size |
| CN103351017A (en) * | 2013-07-01 | 2013-10-16 | 南昌大学 | Preparation method of fine-grained, high-bulk-density, ball-shaped, rare earth carbonate and oxide thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115814751A (en) * | 2022-12-15 | 2023-03-21 | 贵州大学 | Method for preparing porous calcium silicate adsorbent by alkali-activated electrolytic manganese slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106517200B (en) | 2019-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100572286C (en) | Utilize arsenic-containing waste water to prepare the method for white arsenic | |
| CN100469697C (en) | Method for producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution | |
| US11479472B2 (en) | Systems and methods to recover value-added materials from gypsum | |
| CN103395796B (en) | Comprehensive utilization method of serpentine and device used by method | |
| CN106282553A (en) | The smelting separation method of Rare Earth Mine | |
| CN106517621B (en) | Recycling process of ammonium chloride-containing wastewater | |
| CN104016398B (en) | A kind of method that dilute sulfuric acid utilized in industrial wastewater produces sulfate | |
| CN102424391A (en) | Method for comprehensive utilization of aluminum-containing material | |
| CN101760641B (en) | Technology for recovering magnesium from magnesium sulfate solution | |
| WO2020154699A1 (en) | Systems and methods to treat flue gas desulfurization and metal-bearing waste streams to recover value-added materials | |
| US20210347648A1 (en) | Systems and methods to treat flue gas desulfurization and metal-bearing waste streams to recover value-added materials | |
| CN104760979B (en) | A kind of preparation technology of high-purity alumina powder | |
| CN107954474A (en) | A kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution | |
| KR20200108063A (en) | Method for producing high-purity batterite-type and calcite-type calcium carbonate using indirect carbonation of seawater | |
| CN110240201A (en) | A method of processing scheelite | |
| CN104724740B (en) | A kind of preparation method of high pure and ultra-fine aluminium hydrate powder | |
| AU2016318839B2 (en) | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN101760643B (en) | Improved method for recovering magnesium from magnesium sulfate solution | |
| CN111732115A (en) | Preparation method and application of metallurgical precipitation grade magnesium oxide | |
| CN106517200B (en) | The preparation method of metal carbonate | |
| CN114560486B (en) | CO with leaching aid capable of being recycled 2 Indirect mineralization method | |
| CN106517294A (en) | Method for preparing metal oxide | |
| CN103073125B (en) | Method for using acidolysis nickel laterite ore wastewater | |
| CN110357164A (en) | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |