CN106517200B - The preparation method of metal carbonate - Google Patents
The preparation method of metal carbonate Download PDFInfo
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- CN106517200B CN106517200B CN201510571961.2A CN201510571961A CN106517200B CN 106517200 B CN106517200 B CN 106517200B CN 201510571961 A CN201510571961 A CN 201510571961A CN 106517200 B CN106517200 B CN 106517200B
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Abstract
The invention discloses a kind of preparation methods of metal carbonate.The preparation method includes: with solution and CO containing ammonium hydroxide2Gas carries out precipitation reaction to solution of metal sulfates, obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid；The alkaline matter that calcic is added into precipitating waste liquid is recycled, and the alkaline solution containing ammonium hydroxide is obtained；Alkaline solution is returned as the solution containing ammonium hydroxide and is recycled.By utilizing solution and CO containing ammonium hydroxide2Gas carries out precipitation reaction to solution of metal sulfates, can obtain the metal carbonate of different physical property and/or basic metal carbonates and waste liquid be made to change into the preparation for being reused for metal carbonate for the solution containing ammonium hydroxide through alkali.This method combines metal smelt separating technology with waste water treatment, recycles ammonium sulfate waste water while obtaining metal carbonate product salt, and process is short, less energy consumption, at low cost, green low-carbon.
Description
Technical field
The present invention relates to metal smelts and industry environmental protection field, in particular to a kind of system of metal carbonate
Preparation Method.
Background technique
In metal smelt separation production process, various solution of metal sulfates generally use ammonium bicarbonate precipitation and prepare metal
Carbonate can generate a large amount of ammonium sulfate waste waters in preparation process, can generate a large amount of low-concentration sulfuric acid ammoniums particularly by washing process
Waste water.
During metal sulfate prepares metal carbonate, the ammonia nitrogen for the liquid containing ammonium sulfate that ammonium bicarbonate precipitation process generates
Class waste water, since 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, place
Relative difficulty is managed, more difficult, processing cost height is handled using end conventional method.
There is enterprise using the method for sodium carbonate or sodium bicarbonate precipitating replacement ammonium bicarbonate precipitation to solve, but this method is deposited
In Railway Project: (a) price of carbon sodium is higher than ammonium bicarbonate, increases production cost；(b) molecular weight of sodium is bigger than ammonia, and generation is given up
Total salt amount is 1.23 times higher than ammonium salt in water, i.e. the total release of pollutant is not reduced, into underground water after the problem of causing more
It is more；(c) discharge standard of total salt amount in waste water is once put into effect in country or place, it is also necessary to be administered again.
The research and application handled in the circulation and stress of industrial brine waste is upper, and studying at present more is using UF membrane
Concentration method, evaporative crystallization method, vaporizing extract process and break point chlorination etc..Membrane separation process be using selective penetrated property separation water in from
Son, molecule or particle, treatment effect is preferable, but easily causes fouling membrane.Evaporative crystallisation process refers to that brine waste is dense through evaporating
Contracting, reaches hypersaturated state, salt is made to form nucleus in waste water, then gradually generates crystalline solid and then realizes separation, this side
Method is suitable for the processing of high-salt wastewater.Vaporizing extract process, which refers to, allows waste water directly to contact with water vapour, makes the volatile materials in waste water
It is diffused into gas phase by a certain percentage, to achieve the purpose that separate pollutant from waste water, is mainly used for effumability dirt
Contaminate the processing of object.Break point chlorination is that a certain amount of chlorine or sodium hypochlorite are added in waste water, and ammonia nitrogen is made to be oxidized to N2,
To achieve the purpose that remove ammonia nitrogen.It is higher, right that these methods all have high one-time investment, process flow length, operating cost
Waste water quality requires the disadvantages of stringent, and recycling is at high cost, and shipwreck to impure ion complexity, is contained with whole recyclings
The higher ammonium sulfate waste water of calcium ions and magnesium ions is less applicable in, thus application industrially is restricted.
Rise the ammonia nitrogen class waste water that a kind of chemical precipitation method handles such liquid containing ammonium sulfate the 1990s.This method needs
Mg is added2+、PO4 3-And alkaline solution forms double salt MgNH by adjusting pH value4PO4·6H2(MAP, long-acting slow-release are compound by O
Fertilizer).This method is to the removal rate of ammonia nitrogen up to 95% or more, and ammonia-nitrogen content is 20mg/L-40mg/L in treated waste water.But
It is that the ammonia nitrogen removal frank of the method is influenced by ammonia nitrogen concentration initial in waste water, is suitable for high-concentration sulfuric acid ammonium waste water.And locate
The alkalescent waste water that sulfur acid sodium is generated after reason, although solving the problems, such as ammonia nitrogen, without solving discharged wastewater met the national standard and synthesis
The question of substance utilized.
Processing for dilute sulfuric acid ammonium waste water, the U.S. have document report to obtain sulphur ammonium using the method for multistep evaporation, concentration
Solid and removing ammonia.Japan also has patent document to disclose excessive potassium hydroxide or potassium oxide are added into waste water, makes in solution
Sulfate ion as most of potassium sulfate solid precipitating, re-evaporation removes ammonia.It is de- that China has disclosure that magnesium salts is used to do precipitating reagent
Except ammonia nitrogen therein, then adjust pH value condensing crystallizing.The side that solid ammonium sulfate is recycled from dilute sulfuric acid ammonium is separately disclosed there are also patent
Method, first blowing air is by Fe2+Oxide layer Fe3+Remove, then generate dihydrate gypsum and weak aqua ammonia with lime treatment, weak aqua ammonia by from
Son exchange bed adsorption removes ammonia, is regenerated with dilute sulfuric acid to resin after ammonia saturation, obtained dilute sulfuric acid ammonium is neutralized with liquefied ammonia
It is concentrated in vacuo and crystallizes again after to pH value 8.0.The common drawback of the processing method of the above various dilute sulfuric acid ammonium waste water is processing stream
Journey is complicated, and processing cost is high.
Therefore, in terms of the comprehensive reutilization of metal carbonate liquid containing ammonium sulfate waste water produced during the preparation process, it is still necessary to
The prior art is improved, to provide, one kind is cheap, environmentally friendly and treated, and waste water is able to carry out the metal carbon recycled
Hydrochlorate preparation process.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation methods of metal carbonate, to provide a kind of cheap, environmental protection
And treated that waste water is able to carry out the metal carbonate preparation process recycled.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of preparation method of metal carbonate,
The preparation method includes: step S1, using containing ammonium hydroxide solution and carbon dioxide gas to solution of metal sulfates carry out
Precipitation reaction obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid；Step S2 adds into precipitating waste liquid
The alkaline matter for entering calcic is recycled, and the alkaline solution containing ammonium hydroxide is obtained；And step S3, alkaline solution is returned
Step S1 is returned to be recycled as the solution containing ammonium hydroxide.
Further, in step sl, the pH value of precipitation reaction is controlled in 2.0~10.0 ranges.
Further, step S1 includes: step S11: carbon dioxide gas progress is passed through into the solution containing ammonium hydroxide
Carburizing reagent obtains the solution containing ammonium hydrogen carbonate；And step S12: by solution and solution of metal sulfates containing ammonium hydrogen carbonate
Mixing obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid.
Further, step S1 includes: step S11 ': the solution containing ammonium hydroxide is mixed with solution of metal sulfates
It closes, obtains metal alkaline slurries；And step S12 ': it is passed through carbon dioxide gas into metal alkaline slurries and be carbonized instead
It answers, obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid.
Further, step S1 includes: by solution, solution of metal sulfates and carbon dioxide gas containing ammonium hydroxide
Mixing is reacted simultaneously, obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid.
Further, step S11 includes: and is passed through carbon dioxide gas into the solution containing ammonium hydroxide be carbonized instead
It answers, and controls slurries of the pH value of carbonation reaction in 7.0~10.0 ranges, after being carbonized；And to carbonization after
Slurries are separated by solid-liquid separation, and the solution containing ammonium hydrogen carbonate is obtained.
Further, in step s 2, the alkaline matter of calcic is with OH-Meter, OH-Molal quantity and precipitating waste liquid in NH4 +
Molal quantity ratio be 1.00~1.30:1.
Further, step S2 includes: step S21, and the pH value for precipitating waste liquid is adjusted to 3.0 with the alkaline matter of calcic
~6.0, obtain solidliquid mixture；Step S22, is filtered solidliquid mixture, obtains filtrate；And step S23, to filtrate
In continuously add the alkaline matter of calcic, obtain the solution containing ammonium hydroxide.
Further, the alkaline matter of calcic is one or more of calcium hydroxide, calcium oxide and light dolomite.
Further, metal sulfate includes alkali metal sulfates, alkali earth metal sulfate, transition metal sulfate, sulphur
Any one of sour gallium, Ge(SO), STANNOUS SULPHATE CRYSTALLINE and antimony sulfate；It is preferred that transition metal sulfate include sulfuric acid rare earth, zirconium sulfate,
Any one of hafnium sulfate, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate.
Further, carbon dioxide gas roasts kiln gas by gas, the metal carbonate in metal carbonate technology of threonates
And the recycling of one or more of boiler smoke obtains.
Further, in step S2, while obtaining the solution containing ammonium hydroxide, the solid slag of sulfur acid calcium is also obtained；
The solid slag of sulfur acid calcium is purified to obtain calcium sulfate, calcium sulfate is used as the raw material for preparing gypsum or cement.
It applies the technical scheme of the present invention, the solution and carbon dioxide gas by utilization containing ammonium hydroxide are to metal sulfate
Salting liquid carries out precipitation reaction and prepares metal carbonate and/or basic metal carbonates, then molten to the liquid containing ammonium sulfate of generation
The basic species such as the calcium hydroxide slurry (white lime) that precipitating waste liquid calcium hydroxide, calcium oxide or the lime slaking of liquid obtain
Matter carries out alkali and turns recovery processing, obtains the alkaline solution containing ammonium hydroxide；Then again by the alkaline solution containing ammonium hydroxide
As the solution containing ammonium hydroxide, with CO2Gas carries out precipitation reaction to solution of metal sulfates.The preparation method process flow
It is short, waste water treatment is combined with metal smelt separating technology, energy consumption and raw material cost is low, obtain metal carbonate and/
Or while basic metal carbonates product, ammonium sulfate waste water is recycled, and process is short, less energy consumption, at low cost, green is low
Carbon.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows a kind of preparation method flow diagram of the middle metal carbonate of preferred embodiment according to the present invention.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As background technology part is previously mentioned, often generate largely during preparing metal carbonate containing ammonia nitrogen
Waste water, and wastewater treatment method in the prior art exists or treated that waste water can not qualified discharge or treatment process
Complicated, the problems such as processing cost is high.In order to provide a kind of preparation process of cheap, efficient and environmentally friendly metal carbonate, at this
It invents in a kind of typical embodiment, a kind of preparation method of metal carbonate is provided, as shown in Figure 1, the preparation method
Include: step S1, using containing ammonium hydroxide solution and carbon dioxide gas to solution of metal sulfates carry out precipitation reaction, obtain
To metal carbonate and/or basic metal carbonates and precipitating waste liquid；The alkalinity of calcic is added into precipitating waste liquid by step S2
Substance is recycled, and the alkaline solution and step S3 containing ammonium hydroxide are obtained, using alkaline solution return step S1 as
Solution containing ammonium hydroxide is recycled.
Above-mentioned preparation method of the invention, the solution and carbon dioxide gas by utilization containing ammonium hydroxide are to metal sulfate
Salting liquid carries out precipitation reaction and prepares metal carbonate and/or basic metal carbonates, then molten to the liquid containing ammonium sulfate of generation
The basic species such as the calcium hydroxide slurry (white lime) that precipitating waste liquid calcium hydroxide, calcium oxide or the lime slaking of liquid obtain
Matter carries out alkali and turns recovery processing, obtains the alkaline solution containing ammonium hydroxide；Then the alkaline solution by this containing ammonium hydroxide returns
Step S1 is re-used as the solution containing ammonium hydroxide, with CO2Gas carries out precipitation reaction to solution of metal sulfates.The preparation
Method and process process is short, and waste water treatment is combined with metal smelt separating technology, energy consumption and raw material cost is low, is obtaining gold
While belonging to carbonate and/or basic metal carbonates product, nitrogen-containing wastewater is also effectively treated, has realized ammonia nitrogen waste water
It recycles.
Moreover, above-mentioned preparation method of the invention, when the hydrogen-oxygen obtained with calcium hydroxide, calcium oxide or lime slaking
When the alkaline matter of the calcics such as change calcium slurry (white lime) carries out alkali turn recovery processing to the precipitating waste liquid of liquid containing ammonium sulfate, obtaining
While alkaline solution containing ammonium hydroxide, additionally it is possible to obtain the solid slag of sulfur acid calcium, as shown in Figure 1, to the solid slag into
The purification measures such as row acidification, washing can obtain calcium sulfate, and calcium sulfate can be used as preparing the raw material of gypsum or cement.In addition, should
Carbon dioxide gas in preparation method can recycle the CO that metal production process or boiler generate2Gas is not only realized
Application in metal carbonate preparation, and reduce greenhouse gas emission.
In above-mentioned steps S1, according to the difference for the metal sulfate type to be precipitated, control containing the molten of ammonium hydroxide
The amount of liquid and carbon dioxide gas, so that the pH value of precipitation reaction is in suitable range.In a kind of preferred implementation of the invention
In example, the pH value of precipitation reaction is controlled in 2.0~10.0 ranges.By pH value control can cover within the above range it is various not
Same solution of metal sulfates obtains condition when respective metal carbonate and/or basic metal carbonates.
In above-mentioned preparation method of the invention, step S1 is that metal carbonate and/or metal are prepared by metal sulfate
The step of subcarbonate, using containing ammonium hydroxide solution and carbon dioxide gas make metal sulfate occur precipitation reaction
To obtain metal carbonate and/or basic metal carbonates.Thus, in this step, between three in a manner of any kind into
The step of mixture prepared metal carbonate of row and/or basic metal carbonates, is suitable for the present invention.In the present invention one
In kind preferred embodiment, above-mentioned steps S1 includes: step S11: carbon dioxide gas is passed through into the solution containing ammonium hydroxide
Carburizing reagent is carried out, the solution containing ammonium hydrogen carbonate is obtained；And step S12: by solution and metal sulfate containing ammonium hydrogen carbonate
Solution mixing obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid.
The specific reaction equation of above-mentioned steps S11 is as follows:
NH4OH+CO2→NH4HCO3
The specific 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 it is
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 be will contain ammonium hydroxide solution and carbon dioxide gas be initially formed ammonium hydrogen carbonate, then with
Ammonium hydrogen carbonate makes metal sulphate precipitation as precipitating reagent, to obtain metal carbonate and/or basic metal carbonates.Using
Which carries out the preparation of metal carbonate and/or basic metal carbonates, is to prepare ammonium hydrogen carbonate i.e. using carbonizatin method
Activity is higher, keeps precipitation reaction rapider when precipitating metal sulfate as precipitating reagent.Moreover, passing through control carbon dioxide gas
Be passed through and can synthesize compound precipitants, synthesized compound precipitants match different, then the precipitating particle composition for preparing, structure are equal
It is variant.The ammonium bicarbonate soln of solution and carbon dioxide gas containing ammonium hydroxide can also be stored it is spare, or into one
It is spare that step evaporative crystallization prepares the storage of ammonium hydrogen carbonate solid product.
In another preferred embodiment of the invention, above-mentioned steps S1 includes: step S11 ': will be containing the molten of ammonium hydroxide
Liquid is mixed with solution of metal sulfates, obtains metal alkaline solution；And step S12 ': it is passed through into metal alkaline solution
Carbon dioxide gas carries out carburizing reagent, obtains metal carbonate and/or basic metal carbonates and precipitating waste liquid.
The specific reaction equation of above-mentioned steps S11 ' is as follows:
y NH4OH+B(SO4)y/2→B(OH)y+y/2(NH4)2SO4
The specific reaction equation of above-mentioned steps S12 ' is as follows:
B(OH)y+y/2CO2→B(CO3)y/2+y/2H2O；Or it is
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, gold is obtained
Belong to alkaline solution；Then carbon dioxide gas is passed through into metal alkaline solution again and carries out carburizing reagent, obtains metal carbonate
And/or basic metal carbonates and precipitating waste liquid.In the preferred embodiment, metal carbonate and/or basic metal carbonic acid are obtained
Salt be by being carbonized using the carbon dioxide of gas form, and gaseous carbon dioxide compare liquid carbanion,
Facilitate flow velocity and total flow by controlling the carbon dioxide gas being passed through to reach the metal for generating different structure and form
The purpose of carbonate.That is, be conducive to enterprise according to the product category to be prepared and the difference of structure, it can be by metal sulfate
It is prepared into the salt that metal carbonate, basic metal carbonates or both mix in varing proportions, enables adaptation to market pair
The diversified demand of carbonate products.
In another preferred embodiment of the present invention, above-mentioned steps S1 includes: by solution, metal sulphur containing ammonium hydroxide
Acid salt solution and carbon dioxide gas mix simultaneously to be reacted, obtain metal carbonate and/or basic metal carbonates with
And precipitating waste liquid.The preferred embodiment by solution, solution of metal sulfates and carbon dioxide gas containing ammonium hydrogen carbonate simultaneously
Mixing purposive can obtain metal carbonate and/or basic metal carbonic acid of different nature by controlling three's hybrid mode
Salt.The hybrid mode of three can be with are as follows: 1. by containing ammonium hydroxide solution and carbon dioxide gas be passed through in metal salt solution；②
Three is added in the liquid of bottom in a manner of three bursts of cocurrents.3. use tower reaction kettle, carbon dioxide gas and metal salt solution and
Solution containing ammonium hydroxide is fed from different location, and gas-liquid two-phase is mixed in a counter-current configuration.No matter with which kind of hybrid mode,
Mass flow be it is adjustable, by the control to flow and precipitation process, can obtain that there is ultra-fine, epigranular, shape
Metal carbonate/basic metal carbonates of the properties such as looks rule (such as spherical), good dispersion.
The specific 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 it is
2D(SO4)z/2+2z NH4OH+z/2CO2→D2(OH)z(CO3)z/2+z(NH4)2SO4+z/2H2O；
Wherein, Dz+For metal cation.
Be initially formed above-mentioned containing ammonium bicarbonate soln, recycle ammonium bicarbonate soln as precipitating reagent to metal sulfate into
In the preferred embodiment of row precipitation reaction, the solution formed in step S11 containing ammonium hydrogen carbonate is fully able to for metal
Sulfate carries out precipitation reaction.The metal carbonate and/or gold obtained after efficiency and precipitating in order to further increase precipitating
The purity for belonging to subcarbonate, in another preferred embodiment of the invention, above-mentioned steps S11 includes: to containing ammonium hydroxide
Solution in be passed through carbon dioxide gas and carry out carburizing reagent, and control the pH value of carbonation reaction in 7.0~10.0 ranges
It is interior, the slurries after being carbonized；And the slurries after carbonization are separated by solid-liquid separation, obtain the solution containing ammonium hydrogen carbonate.
Since the solution containing ammonium hydroxide is recycled in preparation method of the invention, in order to make to be formed by
Solution containing ammonium hydrogen carbonate is purer, and above preferred embodiment is by being first adjusted to 7.0~10.0 ranges for pH with carbon dioxide
It is interior, so that the micro calcium sulfate that may contain in the solution containing ammonium hydroxide is converted to precipitation of calcium carbonate and is removed, thus
To the higher solution containing ammonium hydrogen carbonate of purity, further precipitating obtains the higher metal carbonate of purity and/or basic metal
Carbonate.
In above-mentioned preparation method of the invention, the step of recovery processing with the alkaline matter of calcic to precipitating waste liquid
In, not only fully consider the reasonable utilization to precipitating this ammonia nitrogen waste water of waste liquid, but also generate after also contemplating recovery processing
Possible waste residue processing.In order to make to be able to carry out and recycle after precipitating the recovered processing of waste liquid, and discharge waste is to ring
Border influence is smaller, and in the another preferred embodiment of the present invention, the alkaline matter of calcic is in above-mentioned steps S2 with OH-Meter, OH-
Molal quantity and waste water in NH4 +Molal quantity ratio be 1.00~1.30:1.Wherein, with OH-Meter, refers to the alkalinity of calcic
The OH that substance can be provided with the form calculus of its hydroxide-。
Specific 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, controlled by the amount of the alkaline matter for the calcic that will be added in above-mentioned suitable range
It is interior, not only made ammonium ion be enough to be completely converted into ammonium hydroxide, but also base excess is avoided to cause solid slag and filtrate alkalinity bigger than normal.Solid slag
When alkalinity is bigger than normal, direct filters pressing stacking can not only make alkalization of soils, and easily pass through harmful components therein (especially alkali composition)
Cross the invasion polluted-water and soil of Weathering And Leaching, rainwash；Filtrate alkalinity it is bigger than normal when, direct emission water body can be caused compared with
Big harm, destroys the ecological balance.It is carried out again to cause equipment larger corrosivity when in-depth processing, and need to be consumed more
Acidic chemical raw material reduces alkalinity.
Above-mentioned steps S2 of the invention is to obtain the same of metal carbonate and/or basic metal carbonates to step S1
When, the step of precipitating waste liquid of the liquid containing ammonium sulfate of generation is recycled, thus, it is any will using the alkaline matter of calcic
The operation that ammonium ion in precipitating waste liquid is converted to the solution (i.e. ammonium hydroxide) containing ammonium hydroxide is suitable for the present invention.In this hair
In another bright preferred embodiment, above-mentioned steps S2 includes: S21, and the pH value tune of waste liquid will be precipitated with the alkaline matter of calcic
Section obtains solidliquid mixture to 3.0~5.0；Step S22, is filtered solidliquid mixture, obtains filtrate；And step
S23 continuously adds the alkaline matter of calcic into filtrate, obtains the solution containing ammonium hydroxide.
Above preferred embodiment, by first using the alkaline matter of calcic to adjust the pH value of the precipitating waste liquid containing ammonium sulfate
To 3.0~5.0, the beavy metal impurities ions such as Fe, Al, Zn, the Cu that may contain in waste liquid will be precipitated by, which helping, is initially formed precipitating
It is effectively removed.The basic species of calcic are continuously added in the filtrate obtained after to heavy metal precipitations such as removing Fe, Al, Zn, Cu
Matter carries out pH value adjusting so that in precipitating waste liquid the calcium ion that may contain form calcium sulfate precipitation in conjunction with sulfate ion and
It is further removed, to obtain the higher solution containing ammonium hydroxide of purity, and then precipitates and obtain the higher metal carbon of purity
Hydrochlorate and/or basic metal carbonates.The recovery processing step has not only been effectively treated complicated ammonia nitrogen waste water, and has realized
The closed cycle of ammonia utilizes, and the consumption of the precipitating reagents such as ammonia is greatly reduced, and be able to achieve the safety of possible solid slag
Emission treatment.
It is recycled to obtain during containing Ammonia in the alkaline matter of above-mentioned addition calcic, it can be with
Ammonia is prepared by stripping, or the finally obtained alkaline solution containing ammonium hydroxide is subjected to stripping and prepares ammonia.It collects back
The ammonia received, and it is used to prepare metal carbon to solution of metal sulfates progress precipitation reaction together with carbon dioxide gas
In the processing step of hydrochlorate or basic metal carbonates, the higher metal carbonate of purity or basic metal carbonates can be obtained.
In above-mentioned preparation method of the invention, the alkaline matter of calcic on the one hand be used to precipitate the ammonium root in waste liquid from
Sub- alkali switchs to ammonium hydroxide；On the other hand for being precipitated the sulfate ion in precipitating waste liquid to form calcium sulphate solid slag.
Thus, the alkaline matter of calcic includes but are not limited to calcium hydroxide, calcium oxide, one in light dolomite in above-described embodiment
Kind is several.The alkaline matter of above-mentioned several calcics has the advantages that cost is relatively low, from a wealth of sources.
Above-mentioned preparation method of the invention, used metal sulfate include but are not limited to alkali metal sulfates, alkali
Any one of earth metal sulfate, transition metal sulfate, gallium sulfate, Ge(SO), STANNOUS SULPHATE CRYSTALLINE and antimony sulfate；It is preferred that transition
Metal sulfate includes any in sulfuric acid rare earth, zirconium sulfate, hafnium sulfate, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate
Kind.
It, not only will be above-mentioned pure or not by above-mentioned metal sulfate by preparing carbonate using preparation method of the invention
Pure metal sulfate is converted to purity and the higher metal carbonate of application value and/or basic metal carbonates, and
Reasonable utilization is carried out to nitrogen-containing wastewater produced during the preparation process, while realizing ammonia closed cycle, to being likely to occur
Solid slag also achieve and be effectively treated.Such as in above-mentioned preparation step S2, while obtaining the solution containing ammonium hydroxide,
Also obtain the solid slag of sulfur acid calcium；The solid slag of sulfur acid calcium is purified to obtain calcium sulfate, which may be used as preparing
The raw material of gypsum or cement.
In above-mentioned preparation method of the invention, the source of carbon dioxide gas can be it is a variety of, either from industrial waste gas
It is middle to recycle obtained carbon dioxide gas, or the carbon dioxide gas of technical grade industrially pure as made from other reactions
Body is suitable for the present invention.From environmental protection and the consideration of energy consumption angle is reduced, carbon dioxide gas of the invention is preferably by metal carbonate
Gas, metal carbonate roasting one or more of kiln gas and boiler smoke recycling in technology of threonates obtain.From upper
Stating the gas generated in several technical process is raw material, by obtaining carbon dioxide gas after compression, purification or other processing steps
Body, had both carried out reasonable utilization to above-mentioned process gas, and low-carbon emission reduction meets environmental requirement；And carbon dioxide gas is realized again
Effective application of body.Angle is utilized from the Efficient Cycle of cost of material, energy consumption, so that above-mentioned preparation method of the invention becomes enterprise
Efficient and low energy consumption the metal carbonate salt production process that industry is really applicable in.
Further illustrate beneficial effects of the present invention below in conjunction with specific embodiments.
Using icp ms, inductive coupling plasma emission spectrograph and atomic absorption spectrophotometry light
Degree meter measures the constant and trace element of product, is measured using granularity of the laser particle analyzer to product.
Embodiment 1
By the lanthanum sulfate cerium solution 10L (concentration 15g/L, in terms of REO) of rare earth extraction separating-purifying and contain ammonium hydroxide
Solution be added in precipitation reactor, while being passed through industrial carbon dioxide gas into precipitation reactor, control reaction process
Middle pH value is maintained between 6.5~7.0 ranges, react continue 3h after obtain lanthanum carbonate cerium slurry, be filtered, wash and
Drying obtains 332.0g artificial lanthanite cerium crystal (REO 45wt%), and the REO rate of recovery is 99.6%；It is obtained by filtration simultaneously
Waste liquid, the as waste water of liquid containing ammonium sulfate.
Calcium oxide is added into the waste water of liquid containing ammonium sulfate, makes the mole of calcium oxide (with OH-Meter) with ammonium sulfate waste water in
The mole ratio of ammonium ion is n (OH-):n(NH4 +)=1.08:1, ammonia radical ion to ammonium hydroxide conversion ratio be 99.0%.Solid-liquid point
From obtaining the solid slag containing Ammonia and sulfur acid calcium.
Alkaline solution containing ammonium hydroxide recycles.The solid slag of sulfur acid calcium obtains calcium sulfate by purification process and produces
Product.
Embodiment 2
By the samarium sulphate solution (concentration 20g/L, in terms of REO) of rare earth extraction separating-purifying and the solution containing ammonium hydroxide
It is passed through from tower reactor top, the flow of samarium sulphate solution is 5m3/h；Carbon dioxide is passed through from tower reactor lower part simultaneously
Gas forms gas-liquid counter current, and controls pH in reaction process and be maintained between 6.5~7.0 ranges, and samaric carbonate slurry is obtained after reaction
Material, be filtered, wash and drying obtain hydration samaric carbonate crystal, yield be 181.3kg/h (REO 55wt%), samarium return
Yield is 99.7%；Recycling precipitating waste liquid, the as waste water of liquid containing ammonium sulfate, carry out processing recycling by embodiment 11 after filtering simultaneously
Obtain the solution reuse containing ammonium hydroxide.
Carbon dioxide gas is that the gas and samaric carbonate in samarium sulphate production technology roast what kiln gas recycled.
The samaric carbonate crystal size is thinner after tested, between 1~3 μm.
Embodiment 3
By the isolated sulfuric acid mixed rare earth solution 10m of rare earth extraction3(concentration 25g/L, in terms of REO) and contain hydrogen-oxygen
The solution for changing ammonium is added in precipitation reaction kettle, while carbon dioxide gas is passed through into precipitation reaction kettle, controls reaction process
Middle pH is maintained between 6.8~7.0 ranges, is reacted and is continued to obtain mixed rare earth carbonate slurry after 4h, is filtered, washs
497.5kg hydration mixed rare earth carbonate crystal (REO 50wt%), rare earth yield 99.5%, while mistake are obtained with drying
Recycling precipitating waste liquid, the as waste water of liquid containing ammonium sulfate after filter carry out processing recycling by embodiment 12 and obtain containing the molten of ammonium hydroxide
Liquid reuse.
Carbon dioxide gas is that the gas and mixed rare earth carbonate in rare-earth smelting separating and producing roast kiln gas recycling
It obtains.
Embodiment 4
First the cerous sulfate 10L (concentration 18g/L, in terms of REO) by purity for 99.99wt% and the solution containing ammonium hydroxide
It is added in precipitation reactor, while being passed through carbon dioxide gas into precipitation reactor, control pH in reaction process and be maintained at
It between 6.2~7.0 ranges, reacts and continues to obtain cerous carbonate slurry after 4h, be filtered, repeatedly washing and drying obtain
344.8g cerium carbonate hydrate crystal (REO 52wt%), the rate of recovery of cerium are 99.6%；Recycling precipitating waste liquid after filtering simultaneously,
The as waste water of liquid containing ammonium sulfate carries out processing recycling by embodiment 13 and obtains the solution reuse containing ammonium hydroxide.
It is few due to recycling the impurity contents such as Fe, Si in the obtained solution containing ammonium hydroxide, and the cerous carbonate formed is brilliant
Type is good, can obtain purity by repeatedly washing as 99.99wt% carbonic acid cerium crystal.
Comparative example 1
Ammonium hydrogencarbonate is added in the cerous sulfate 10L (concentration 18g/L, in terms of REO) that purity is 99.99wt% and precipitates carbon
Sour cerium, control are reacted between the range of pH=6.2~7.0；It is separated by solid-liquid separation, obtains the cerous carbonate and contain that purity is 99.95wt%
The waste water of ammonium sulfate.
Since ammonium hydrogen carbonate has brought the impurity such as Fe, Si, Al into, cerous carbonate purity is affected.
Embodiment 5
First by the cerous sulfate solution 10L (concentration 15g/L, in terms of REO) of rare earth extraction separating-purifying and containing ammonium hydroxide
Solution be added in precipitation reactor and react, then carbon dioxide gas is passed through into precipitation reactor, during W-response
Control pH is maintained between 6.2~7.0 ranges, and temperature is maintained between 50 DEG C~60 DEG C, is reacted and is continued to obtain carbon after 4h
Sour cerium slurry is filtered, washs and drying obtains 287.3g carbonic acid cerium crystal (REO 52wt%), and the rate of recovery of cerium is
99.6%；After tested, the cerous carbonate crystal size is larger, between 15~25 μm.Recycling precipitating waste liquid after filtering simultaneously, as
The waste water of liquid containing ammonium sulfate carries out processing recycling by embodiment 13 and obtains the solution reuse containing ammonium hydroxide.
Wherein, because the solution containing ammonium hydroxide is to use method shown in embodiment 13 to the waste water oxygenation of liquid containing ammonium sulfate
To change calcium and carries out what processing recycling obtained, exothermic heat of reaction makes the solution temperature containing ammonium hydroxide being prepared have certain temperature,
Carry out the energy that external heating can be reduced when precipitation reaction.
Embodiment 6
It takes zirconyl chloride solution 10L (concentration 100g/L) to be added in precipitation reactor, is passed through into precipitation reactor
Ammonium hydroxide reaches 2.0~2.8 to system pH, is then passed through solution and technical grade two containing ammonium hydroxide into precipitation reactor simultaneously
Carbon oxide gas is reacted；Reaction system is open normal pressure in reaction process, and carburizing reagent continues to obtain carbonic acid after 3h
Zirconium slurry is filtered, washs and drying obtains zirconium carbonate, and the rate of recovery of zirconium is 99.5% (in terms of zirconium oxide)；It filters simultaneously
Recycling filtering waste liquid, as ammonium sulfate waste water afterwards carry out processing recycling by embodiment 13 and obtain the solution reuse containing ammonium hydroxide.
Embodiment 7
First by the cobalt sulfate solution 10L of rare earth extraction separating-purifying (concentration 50g/L, in terms of REO) and containing ammonium hydroxide
Solution be added in precipitation reactor and react, then carbon dioxide gas is passed through into precipitation reactor, during W-response
Control pH be maintained between 9.5~10.0 ranges, react continue 6h after obtain cobalt carbonate slurry, be filtered, wash and
Drying obtains cobalt carbonate crystal, and the rate of recovery of cobalt is 99.5% (in terms of cobalt oxide)；Recycling precipitating waste liquid after filtering simultaneously, as
The waste water of liquid containing ammonium sulfate carries out processing recycling by embodiment 13 and obtains the solution reuse containing ammonium hydroxide.
Embodiment 8
Carbon dioxide gas is passed through in Ammonia, control is pH=9.5~10.0 in carbonation reaction, will
The composite precipitation agent solution containing ammonium hydrogen carbonate is obtained by filtration in the slurries of formation.By its with nickel sulfate solution 10L (concentration 35g/L,
In terms of nickel oxide) it is added in precipitation reactor and reacts, pH=8.2~10.0 are controlled in reaction process, reaction temperature control exists
Within the scope of 45~50 DEG C；It is separated by solid-liquid separation, obtains 581.0g basic nickel carbonate (NiO 60wt%), the rate of recovery of nickel is
99.6%；Recycling precipitating waste liquid, the as waste water of liquid containing ammonium sulfate after filtering simultaneously carry out processing recycling by embodiment 14 and are contained
The solution reuse of ammonium hydroxide.
Wherein, because the solution containing ammonium hydroxide is to add calcium oxide to carry out processing recycling to the waste water of liquid containing ammonium sulfate to obtain,
Exothermic heat of reaction makes the solution temperature containing ammonium hydroxide being prepared have certain temperature, external need not add when carrying out precipitation reaction
Heat.
Embodiment 9
Industrial carbon dioxide gas is passed through in Ammonia, in carbonation reaction control be pH=7.0~
8.0, the slurries of formation are obtained by filtration to the composite precipitation agent solution containing ammonium hydrogen carbonate.By it, (concentration is with praseodymium sulfate solution 10L
20g/L, in terms of nickel oxide) it is added in precipitation reactor and reacts, pH=6.2~6.8 are controlled in reaction process；It is filtered, is obtained
To 398.8g praseodymium carbonate, the rate of recovery of praseodymium is 99.7%；Recycling precipitating waste liquid, the as waste water of liquid containing ammonium sulfate after filtering simultaneously,
Processing recycling, which is carried out, by embodiment 14 obtains the solution reuse containing ammonium hydroxide.
Embodiment 10~17 is the specific embodiment of waste water recycling device
Embodiment 10~17 is with metal carbonate and/or basic metal carbonates liquid containing ammonium sulfate produced during the preparation process
Waste water is raw material, and the alkaline matter of calcic is added, and on the basis of the mole of ammonium ion in ammonium sulfate waste water, is proportionally added into
Ammonium ion is converted ammonium hydroxide by the alkaline matter of calcic, and separation of solid and liquid obtains the alkaline solution containing ammonium hydroxide and contains
The solid slag of calcium sulfate；
Alkaline solution containing ammonium hydroxide continues to recycle；
The solid slag of sulfur acid calcium obtains calcium sulfate product by purification process.
Specific recovery processing situation is as shown in table 1:
Table 1:
The step of waste water recycling device in embodiment 18~20, is as follows.
Using the waste water of the liquid containing ammonium sulfate of embodiment 6 as raw material, the waste water of liquid containing ammonium sulfate is adjusted with the alkaline matter of calcic
PH value is separated by solid-liquid separation, and the elements such as Fe, Al, the heavy metal ion in waste liquid are removed.Continue to add into the waste water of containing ammonium chloride
Enter calcium oxide.On the basis of the mole of ammonium ion in ammonium sulfate waste water, it is proportionally added into the alkaline matter of calcic, by ammonium root
Ion conversion is ammonium hydroxide.Separation of solid and liquid obtains the solid slag of alkaline solution and sulfur acid calcium containing ammonium hydroxide.
Alkaline solution containing ammonium hydroxide continues to be recycled using the step in embodiment 6.
The solid slag of sulfur acid calcium obtains calcium sulfate product by purification process.
The specific response situation of embodiment 18~20 is as shown in table 2 below:
Table 2:
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
(1) by using containing ammonium hydroxide solution and carbon dioxide gas to solution of metal sulfates progress precipitation reaction
Metal carbonate and/or basic metal carbonates are prepared, then to the precipitating waste liquid hydrogen-oxygen of the liquid containing ammonium sulfate solution of generation
Change the alkaline matters such as calcium, the calcium hydroxide slurry (white lime) that calcium oxide or lime slaking obtain and carry out alkali turn recovery processing,
Obtain the alkaline solution containing ammonium hydroxide；Then the alkaline solution containing ammonium hydroxide is re-used as containing the molten of ammonium hydroxide
Liquid, with CO2Gas carries out precipitation reaction to solution of metal sulfates.The preparation method process flow is short, by waste water treatment and gold
Belong to and smelt separating technology and combine, energy consumption and raw material cost is low is obtaining metal carbonate and/or basic metal carbonates produce
While product, nitrogen-containing wastewater has also been effectively treated, has realized recycling for ammonia nitrogen waste water.
(2) hydroxide that above-mentioned preparation method of the invention can be obtained with calcium hydroxide, calcium oxide or lime slaking
The alkaline matter of the calcics low in cost, from a wealth of sources such as calcium slurry (white lime) carries out alkali to the precipitating waste liquid of liquid containing ammonium sulfate
Turn recovery processing, while obtaining the alkaline solution containing ammonium hydroxide, additionally it is possible to the solid slag of sulfur acid calcium is obtained, it is solid to this
Body slag, which carries out purifying, can obtain calcium sulfate, and calcium sulfate can be used as preparing the raw material of gypsum or cement.In addition, in the preparation method
Carbon dioxide gas, the CO that metal production process or boiler generate can be recycled2Gas is not only realized in metal carbon
Application in hydrochlorate preparation, and reduce greenhouse gas emission.
(3) technique is not high to the component requirements of liquid containing ammonium sulfate waste water, can handle impure ion is complicated, calcium-magnesium-containing from
The waste water of son.
It (4), can be by the impurity gold in waste water with the alkaline matter of calcic by the pH value adjustment process of the waste liquid containing precipitating
Belonging to the beavy metal impurities ion conversions such as ion such as Fe, Al, Cu, Zn is that precipitating is removed through being separated by solid-liquid separation, and can pass through subsequent processing
Purer calcium sulfate product is obtained, property is stablized, and on environment without influence, can be used for cement and the preparation of other construction materials.
(5) by recovery process exhaust gas (exhaust gas in metal carbonate technology of threonates, metal carbonate roast kiln gas and
Boiler smoke) in CO2Gas is carbonized, and reduces greenhouse gas emission, realizes low-carbon emission.
It can be seen that the preparation method of metal carbonate of the invention had both realized the diversification preparation of metal carbonate,
And it realizes the comprehensive of waste water in technical process and is recycled, and be able to achieve the nearly zero-emission of industrial wastewater, exhaust gas and/or waste
It puts, entire process route resource utilization is high, and economic benefit and social benefit are all fairly obvious.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of preparation method of metal carbonate, which is characterized in that the preparation method includes:
Step S1, using containing ammonium hydroxide solution and carbon dioxide gas to solution of metal sulfates carry out precipitation reaction, obtain
To metal carbonate and/or basic metal carbonates and precipitating waste liquid；
Step S2, the alkaline matter that calcic is added into the precipitating waste liquid are recycled, and the alkali containing ammonium hydroxide is obtained
Property solution；And
The alkaline solution is returned to the step S1 as the solution containing ammonium hydroxide and recycled by step S3,
The step S2 includes:
The pH value of the precipitating waste liquid is adjusted to 3.0~6.0 with the alkaline matter of the calcic, it is mixed to obtain solid-liquid by step S21
Close object；
Step S22 is filtered the solidliquid mixture, obtains filtrate；And
Step S23 continuously adds the alkaline matter of the calcic into the filtrate, obtains the solution containing ammonium hydroxide.
2. preparation method according to claim 1, which is characterized in that in the step S1, control the precipitation reaction
PH value in 2.0~10.0 ranges.
3. preparation method according to claim 1, which is characterized in that the step S1 includes:
Step S11: it is passed through carbon dioxide gas into the solution containing ammonium hydroxide and carries out carburizing reagent, obtains containing bicarbonate
The solution of ammonium；And
Step S12: the solution containing ammonium hydrogen carbonate is mixed with the solution of metal sulfates, obtains the metal carbonate
And/or basic metal carbonates and the precipitating waste liquid.
4. preparation method according to claim 1, which is characterized in that the step S1 includes:
Step S11 ': the solution containing ammonium hydroxide is mixed with the solution of metal sulfates, obtains metal alkaline
Slurries；And
Step S12 ': it is passed through carbon dioxide gas into the metal alkaline slurries and carries out carburizing reagent, obtains the metal carbon
Hydrochlorate and/or basic metal carbonates and the precipitating waste liquid.
5. preparation method according to claim 1, which is characterized in that the step S1 includes: by described containing ammonium hydroxide
Solution, the solution of metal sulfates and carbon dioxide gas simultaneously mix reacted, obtain the metal carbonate
And/or basic metal carbonates and the precipitating waste liquid.
6. preparation method according to claim 3, which is characterized in that the step S11 includes:
It is passed through carbon dioxide gas into the solution containing ammonium hydroxide and carries out carburizing reagent, and controls the carburizing reagent
Slurries of the pH value of journey in 7.0~10.0 ranges, after being carbonized；And
Slurries after the carbonization are separated by solid-liquid separation, the solution containing ammonium hydrogen carbonate is obtained.
7. preparation method according to claim 1, which is characterized in that in the step S2, the basic species of the calcic
Matter is with OH-Meter, the OH-Molal quantity and the precipitating 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, which is characterized in that the alkaline matter of the calcic is
One or more of calcium hydroxide, calcium oxide and light dolomite.
9. preparation method according to claim 1, which is characterized in that the metal sulfate include alkali metal sulfates,
Any one of alkali earth 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 in sulfuric acid rare earth, zirconium sulfate, hafnium sulfate, nickel sulfate, cobaltous sulfate, copper sulphate and zinc sulfate
It is any.
10. preparation method according to claim 1, which is characterized in that the carbon dioxide gas is given birth to by metal carbonate
Gas, metal carbonate roasting one or more of kiln gas and boiler smoke recycling in production. art obtain.
11. preparation method according to claim 1, which is characterized in that in the step S2, obtain it is described containing hydroxide
While the solution of ammonium, the solid slag of sulfur acid calcium is also obtained；The solid slag of the sulfur acid calcium is purified to obtain calcium sulfate, institute
It states calcium sulfate and is used as the raw material for preparing gypsum or cement.
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