CN106517294A - Method for preparing metal oxide - Google Patents
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- CN106517294A CN106517294A CN201510572391.9A CN201510572391A CN106517294A CN 106517294 A CN106517294 A CN 106517294A CN 201510572391 A CN201510572391 A CN 201510572391A CN 106517294 A CN106517294 A CN 106517294A
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Abstract
The invention discloses a method for preparing a metal oxide. The method comprises the steps: carrying out a precipitation reaction on a metal salt solution by using ammonia gas and gas carbon dioxide, and controlling the mass ratio of the ammonia gas to the carbon dioxide to the metal salt solution to enable the pH value of the mixture system to 2.0 to 10.0, so as to obtain slurry; carrying out solid-liquid separation on the slurry, so as to obtain ammonium ion containing waste liquor and metal carbonate and/or basic metal carbonate; and carrying out roasting on the metal carbonate and/or basic metal carbonate, thereby obtaining the metal oxide and carbon dioxide containing exhaust gases, wherein the ammonia gas is obtained through adjusting the pH of the ammonium ion containing waste liquor by an alkaline substance and carrying out stripping enrichment. The metal oxide product with different crystal forms, particle sizes and morphologies are obtained in a controlled manner through a gas-liquid reaction and adjusting the mass ratio of the three kinds of raw materials; and the ammonia gas is recycled through wastewater recovery, and gas CO2 can also be recycled through exhaust gas recovery, so that the method has the advantages of short flows, low raw material cost, closed ammonium cycle, low carbon, environment-friendliness and controllable product performance.
Description
Technical field
The present invention relates to field of hydrometallurgy, in particular to a kind of preparation method of metal-oxide.
Background technology
At present, the conventional method for preparing metal-oxide in commercial production is Chemical liquid deposition, i.e., with metal compound solution
For raw material, which is mixed with precipitant solution, form insoluble metal hydroxidess, carbonate or oxalates etc., Jing Guogao
Temperature is decomposed or dehydration obtains respective metal oxide.The conventional precipitant of Chemical liquid deposition includes：Ammonium class precipitant is (main
Including ammonium carbonate, ammonium hydrogen carbonate and ammonia)；Alkali metal hydroxide, carbonate and bicarbonate precipitant (are primarily referred to as hydrogen-oxygen
Change sodium, sodium carbonate and sodium bicarbonate etc.)；Oxalic acid precipitation agent etc., this three classes precipitant are belonged in it there is liquid phase reaction course
Reactive liquid solution, properties of product are affected very big by system degree of supersaturation in course of reaction, are susceptible to that local degree of supersaturation is too high to draw
Play powder granularity uneven, properties of product are difficult to meet application requirement.Meanwhile, this three classes precipitant also exist ammonia nitrogen, high sodium salt,
Oxalic acid wastewater problem, and alkali metal hydroxide, carbonate and bicarbonate precipitant then easily cause the low problem of product purity.
Additionally, the metal carbonate obtained after precipitation and metal oxalate need roasting to obtain rare earth oxide, substantial amounts of by-product will be produced
Thing carbon dioxide greenhouse gas, at present, the industry is to CO2The discharge of greenhouse gases not yet proposes effective solution.
There is Chinese patent application to disclose using inorganic metal salt as raw material, metal component passes through metal inorganic saline solution and organic
Amine reacts, and produces precipitation, and in precipitation process, adds one or more organic compound to prepare nano metal oxygen as stabilizer
Compound.The method is with organic amine as precipitant, and adds organic compound as stabilizer, can produce in a large number containing ammonia and COD
Waste water, while, it is difficult to avoid the non-homogeneous phase deposition in liquid phase reaction course.
Additionally, also Chinese patent document report, the nitric acid or aqueous hydrochloric acid solution with rare earth as raw material, be directly added into carbonate or
It is passed through carbon dioxide to be precipitated；Or with nitric acid or dissolving with hydrochloric acid rare earth oxide, rare earth ion concentration control 0.1～
0.4mol/L, adds carbonate or carbon dioxide to be precipitated.This two patent applications are making using carbon dioxide as precipitant
Standby rare earth oxide.But as the reaction raw materials used by the preparation method are rare earth nitrate prepared by Jing nitric acid or dissolving with hydrochloric acid
Or chloride salt, the solution system acidity is very high, during real reaction, is passed directly into the basic nothing of carbon dioxide gass precursor reactant
Method obtains metal carbonate.
In view of the above problems, it would be highly desirable to propose a kind of environment-friendly preparation method thereof of high-quality metal-oxide, while solving industrial at present
The ammonia-containing water being widely present and CO2The problem that greenhouse gases are discharged in a large number.
The content of the invention
Present invention is primarily targeted at a kind of preparation method of metal-oxide is provided, to solve metal oxidation of the prior art
Ammonia nitrogen waste water and greenhouse gas emission etc. present in thing preparation process cause the problem of environmental pollution, so as to realize that non-ferrous metal is wet
The green of method metallurgy industry, low-carbon (LC), cycle development.
To achieve these goals, according to an aspect of the invention, there is provided a kind of preparation method of metal-oxide, the system
Preparation Method includes：Step S1, carries out precipitation using ammonia and carbon dioxide to metal salt solution, and controls three's
Mass ratio makes the pH value of mixed system in the range of 2.0～10.0, obtains serosity；Step S2, carries out solid-liquid separation to serosity,
Obtain the waste liquid containing ammonium ion and metal carbonate and/or basic metal carbonates；And step S3, to metal carbonate and
/ or basic metal carbonates carry out roasting, obtain the waste gas of metal-oxide and carbon dioxide containing gas；Wherein, ammonia is by containing ammonium
The waste water of radical ion Jing after alkaline matter adjusts pH strips enrichment and obtains.
Further, metal salt solution is the mixed solution of individual metal salt solution or various metals saline solution.
Further, in step S1, ammonia is 1.2 with the mass ratio of carbon dioxide:1～1:4.
Further, ammonia is obtained as follows：To containing ammonium ion waste water in add alkaline matter adjust pH to
3.0～6.0, obtain solidliquid mixture；Solid-liquid separation is carried out to solidliquid mixture, filtrate is obtained；Alkalescence is continuously added in filtrate
Material, obtains ammonia；Stripping enrichment is carried out to ammonia, ammonia is obtained.
Further, in step S1, it is 0.1～0.95MPa to control mixed system in pressure, under conditions of temperature is 10～95 DEG C
Continue 0.5～4 hour.
Further, in step S1, metal salt solution includes that alkali metal salt soln, alkaline-earth metal salt solution, transition metal salt are molten
Any one in liquid, gallium saline solution, germanium saline solution, tin-salt solution and antimonic salt solution.
Further, alkali metal salt soln includes sodium salt solution；Alkaline earth metal solution includes calcium salt soln or magnesium salt solution；Transition
Metal salt solution includes rare earths salt, zirconium salt solution, hafnium saline solution, cobalt salt solution, nickel salt solution, copper salt solution and zinc
Any one in saline solution.
Further, metal salt solution is chloride solution, nitrate solution, sulfate liquor, Acetate Solution and high chlorine
In acid salt solution any one or more.
Further, carbon dioxide is technical grade carbon dioxide or is obtained by the waste gas recovery of carbon dioxide containing gas,
The waste gas of carbon dioxide containing gas is the carbon dioxide that obtains and/or metal carbonate precipitate gas, metal carbonate in step S3
One or more in salt roasting kiln gas, oxalates roasting kiln gas and boiler smoke.
Further, waste water containing ammonium ion is the waste water that produces in industrial processes, the waste water bag that industrial processes are produced
The waste water that the waste water and/or precipitated metal process for including metal extraction separation process generation is produced；Wherein, precipitated metal process is produced
The waste liquid containing ammonium ion that waste water is obtained in including step S2.
Further, alkaline matter is calcium hydroxide, calcium oxide, magnesium oxide, magnesium hydroxide, light dolomite, sodium hydroxide
And one or more in potassium hydroxide, preferably alkaline matter is calcium oxide or sodium hydroxide.
Further, step S3 includes：Metal carbonate and/or basic metal carbonates are placed in into 400 DEG C～1100 DEG C of high temperature
Lower roasting 0.5～12 hour, obtains the waste gas of metal-oxide and carbon dioxide containing gas.
Using technical scheme, by by metal salt solution and ammonia and CO2Gas mixing, is prepared by gas liquid reaction
Metal-oxide, by adjusting metal salt solution with ammonia and CO2The mass ratio of gas so that the pH of reaction system is controllable, enters
And can be constituted, the metal carbonate of structure, pattern or subcarbonate, it is fired to obtain different crystal forms, granularity and shape
The metal oxide products of looks.In the preparation process in accordance with the present invention, ammonia is obtained by waste water recycling device, and carbon dioxide is same
Sample is obtained by waste gas recovery or for industrial grade carbon-dioxide, and, waste water and waste gas can produced by above-mentioned preparation process,
Can also be produced by other processing steps in commercial production.Thus, the preparation method of the present invention has whole preparation process stream
Journey is short, ammonium closed circulation, and cost of material is low, the advantage that low-carbon environment-friendly and properties of product are controllable.
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 metal-oxide in a kind of preferred embodiment of the invention；
Fig. 2 shows the preparation method schematic flow sheet of metal-oxide in another kind of preferred embodiment of the invention；
Fig. 3 shows cerium oxide powder SEM figures in embodiment 3；
Fig. 4 shows cerium carbonate powder SEM figures in embodiment 4；
Fig. 5 shows cerium oxide powder SEM figures in embodiment 4；And
Fig. 6 shows Zirconium powder SEM figures in embodiment 7.
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.
Environmental pollution is caused for ammonia nitrogen waste water and greenhouse gas emission etc. present in metal-oxide preparation process in prior art
Problem, in a kind of typical embodiment of the present invention, there is provided a kind of preparation method of metal-oxide, as shown in figure 1,
The preparation method includes：Step S1, carries out precipitation using ammonia and carbon dioxide to metal salt solution, and controls three
The mass ratio of person makes the pH value of mixed system in the range of 2.0～10.0, obtains serosity；Step S2, carries out solid-liquid point to serosity
From obtaining the waste liquid containing ammonium ion and metal carbonate and/or basic metal carbonates；And step S3, to metal carbonate
Salt and/or basic metal carbonates carry out roasting, obtain the waste gas of metal-oxide and carbon dioxide containing gas；Wherein, ammonia by
Waste water containing ammonium ion Jing after alkaline matter adjusts pH strips enrichment and obtains.
The preparation method of the above-mentioned metal-oxide of the present invention, by by metal salt solution and ammonia and CO2Gas mixing, passes through
Gas liquid reaction prepares metal-oxide, by adjusting metal salt solution, ammonia, CO2The mass ratio of gas so that reaction system
PH is controllable, and then can obtain the metal carbonate or subcarbonate of different physical property, it is fired obtain different crystal forms, granularity and
The metal oxide products of pattern.In the preparation method, ammonia is obtained by waste water recycling device, and carbon dioxide equally may be used
To be obtained by waste gas recovery or as industrial grade carbon-dioxide, and, waste water and waste gas can produced by above-mentioned preparation process,
Can also be produced by other processing steps in commercial production.Thus, the preparation method of the present invention has whole preparation process stream
Journey is short, ammonium closed circulation, and cost of material is low, the advantage that low-carbon environment-friendly and properties of product are controllable.
In above-mentioned steps S1 of the present invention, the effect of ammonia and carbon dioxide is as follows：1. adjust carbonization system pH；2. make
For synthesizing the raw material of metal carbonate and/or basic metal carbonates；3. by adjust ammonia and carbon dioxide relative usage,
The mode of being passed through can be adjusted to the metal-oxide crystal formation of preparation, pattern, granularity, pore structure.In actual fabrication process,
Crystal structure adjusting agent can be added to control the growth rate of each crystal face so as to control formed metal-oxide crystal formation, specific crystal formation is adjusted
Section agent include but are not limited to crystal formation metal carbonate, polyacrylic acid, sodium pyrophosphate, the alkaline metal salt of EDTA, EDTA,
One or more in triethanolamine and mineral acid, the typically not greater than control of addition, the 5% of gained metal oxide weight.
Additionally, after carburizing reagent terminates, dispersant can be added to adjust particle surface electric charge, to obtain the metal carbonate of good dispersion
And/or basic metal carbonates, so as to further be conducive to obtaining the metal-oxide of different physical property.The species of conventional dispersant
Including polycarboxylate sodium, polyacrylic acid sodium salt, molecular weight be the Polyethylene Glycol of 600-10000, the one kind in dodecyl sodium sulfate
Or its mixture；The feed postition of dispersant directly can be added to whole reaction system after carburizing reagent, filter after be added to gold
In category carbonate and/or basic metal carbonates wet cake；The addition of dispersant is typically not greater than gained metal oxide weight
5%.
The feed postition of above two gas can be selected to add slaine according to the be intended to product category for preparing or the difference of structure
In the liquid of in solution or bottom, or cocurrent is added simultaneously with other raw materials.
The chemical equation that above-mentioned steps S1 occur is as follows：
Mz++zNH3+z/2CO2+z/2H2O→M(CO3)z/2+zNH4 +；Or be
2Mz++2zNH3+z/2CO2+3z/2H2O→M2(OH)z(CO3)z/2+2zNH4 +；
Wherein, Mz+For metal cation.
The chemical equation that above-mentioned steps S3 occur is as follows：
Or be
For the recycling step of the waste water containing ammonium ion in above-mentioned preparation method, pH, Jing is adjusted by adding alkaline matter
Reaction heat or exterior-heat is crossed, enriching and recovering ammonia can be stripped.Concrete reaction equation is as follows：
xNH4 ++A(OH)x→xNH4OH+Ax+；Or, 2xNH4 ++A2Ox+x H2O→2xNH4OH+2Ax+；
Wherein, A (OH) x/A2O x are alkaline matter, using reaction heat and/or mode of heating, make Ammonia escape ammonia；
NH4OH→NH3↑+H2O。
Above-mentioned steps can produce saliferous serosity while ammonia is reclaimed, and this serosity can be Jing after solid-liquid separation, respectively to filtrate and admittedly
Body slag is recycled.
When variable concentrations waste water containing ammonium ion is processed, the ammonia concentration of recovery has differences, and can use when ammonia concentration >=50%
In carburizing reagent；Equally, for the carbon dioxide of separate sources, the concentration of recovery has differences, and works as carbon dioxide
Carburizing reagent is used equally to during concentration >=50%.Additionally, as shown in Fig. 2 carbon dioxide is except being produced using step S3
Outside raw carbonated waste gas, other metal carbonate precipitate gases, metal carbonate roasting kiln gas, grass can also be utilized
One or more in hydrochlorate roasting kiln gas and boiler smoke；Can also be the next technical grade carbon dioxide of directly purchase.
Technical grade carbon dioxide refers to commercially available carbon dioxide, and its purity is more than 99.8%, and preparation method can be high-temperature heating stone
Lime stone decomposition obtains carbon dioxide, and equation is
It is above-mentioned by containing ammonium ion waste water reclamation ammonia the step of include：To in the waste water containing ammonium ion alkaline matter is added to adjust
Section pH value obtains Ammonia to 3.0～6.0；Ammonia carries out stripping enrichment by reaction heat and/or external heat,
Obtain ammonia.For preventing also containing heavy metal heteroions such as Fe, Al, Zn and Cu in the waste water containing ammonium ion, first by pH
These heteroions can be formed precipitation and be removed in the range of 3.0～6.0 by value control；It is then followed by plus alkaline matter so that phase
Ammonia is converted into the ammonium ion in pure waste water, alkaline matter add waste water in produced by reaction heat and/
Or under the stripping enrichment of external heat, obtain ammonia.
In the above-mentioned preparation method of the present invention, metal salt solution goes for individual metal salt solution, it is also possible to suitable for many
Plant the mixed solution of metal salt solution.
In above-mentioned steps S1, metal salt solution, ammonia, the hybrid mode of carbon dioxide can be：1. by ammonia, titanium dioxide
Carbon gas is passed through in metal salt solution；2. three is added in the liquid of bottom in the way of three bursts of cocurrents；3. tower reactor, gold are adopted
Category saline solution is fed from diverse location with ammonia, carbon dioxide, and gas-liquid two-phase is mixed in a counter-current configuration.No matter with which
The flow for planting hybrid mode, gas flow and metal salt solution is adjustable.If taking the second way, first can control
Ammonia and carbon dioxide are passed through in the liquid of bottom and synthesize compound precipitantses, controlled the different flow of ammonia and carbon dioxide, closed
Into compound precipitantses proportioning it is different, then the precipitation granule composition for preparing and structure it is variant.
The mixed process of above-mentioned steps S1 can select appropriate mixing according to the difference of the species of the be intended to product for preparing and structure
Mode, in a kind of preferred embodiment of the invention, the mass ratio for preferably controlling ammonia with carbon dioxide is 1.2:1～1:4.
When mixing to ammonia and carbon dioxide, can be using mass flowmenter by controlling ammonia and carbon dioxide
Mass ratio is regulating and controlling the morphosiss of prepared product.The relative mass of ammonia and carbon dioxide is adjusted, is on the one hand helped
PH value in regulation and control course of reaction, so that affect to precipitate composition, granularity and the surface electriferous state of granule；On the other hand can give birth to
Into different structure, the carbonate of composition or subcarbonate, so as to regulate and control crystal formation, the pattern of oxide；Another further aspect can be generated
The presoma of nucleocapsid or multiple structure composition, can prepare the oxide powder material of special pore passage structure through pyrolytic.It is intended to
The difference of the metal carbonate and/or basic metal carbonates product of preparation, ammonia are different with carbon dioxide gass body mass ratio.And
For some metal ions, especially transition metal ionss, its basic metal carbonates species is more, and such as zirconium oxycarbonate can be deposited
In following various ways：Zr2(OH)2CO2·nH2O、ZrO2CO2·nH2O、Zr(OH)2CO2·nH2O and
ZrOCO3·nH2O.In continuous mixed process, the mass ratio for controlling ammonia with carbon dioxide is 1.2:1～1:4 can expire
Foot prepares the corresponding various metals carbonate of most metals saline solution and/or basic metal carbonates.To ammonia and carbon dioxide gass
Before body is mixed, one of which gas can also be first passed through, adjustment system pH is to metal carbonate and/or basic metal carbon
PH needed for hydrochlorate precipitation.
Above-mentioned metal salt solution, ammonia, the mixed process of carbon dioxide can be continuous mixing, alternatively intermittent mixing.
Metal salt solution, ammonia, carbon dioxide are carried out into intermittent mixing, is intermittently mixed into ammonia and carbon dioxide gass
Body is mixed in being intermittently passed through mixed system simultaneously, or, intermittently it is mixed into ammonia and carbon dioxide gass body phase
Mixed in being mutually alternately passed through mixed system.
When ammonia and carbon dioxide are intermittently passed through simultaneously mixed in mixed system when；As above-mentioned metal is aoxidized
The preparation method of thing belongs to gas-liquid two-phase reaction, and the precipitating ion that course of reaction is produced is present in gas phase, and its diffusion needs the time；
Meanwhile, intermittence is passed through and the precipitation granule for first generating can also be made to have enough time forming core and grow up to a certain extent, plays crystal seed work
With induction crystallization reduces the forming core energy needed for post precipitation, when continuing to be passed through gas, precipitates the grain surface that can be previously generated
Occur, so as to improve the degree of crystallinity of precipitation granule.
Due in actual application, especially catalytic applications, pore structure often to metal-oxide, multiple structure
Aspect has particular/special requirement, but at present, adopts template the preparation of the metal-oxide of both structures more, and production cost is high, right
Equipment requirements are high, can also produce a large amount of high-COD waste waters.And pass through by ammonia and alternateing property of carbon dioxide be passed through it is mixed
Fit system, can prepare the metal-oxide with loose structure or multiple structure.Ammonia and alternateing property of carbon dioxide ground
It is passed through, by the time in control interval, makes precipitation granule that there are metal hydroxidess, metal carbonate and/or basic metal carbonates
Multiple structure.And then in roasting process, decompose temperature according to metal hydroxidess, metal carbonate and/or basic metal carbonates
The diversity of degree, and the CO of metal carbonate and/or basic metal carbonates decomposition release2The pore-creating effect that gas is played, makes
Metal-oxide has loose structure and/or multiple structure.For mixed salt solution system, precipitated according to different metal ions
The difference of required pH, is alternately passed through ammonia and carbon dioxide, can also prepare with loose structure and/or multilamellar
The metal composite oxide of structure.
In the above-mentioned preparation method of the present invention, particular/special requirement is had no to the pressure in reaction system in step S1, as long as can make
Metal salt solution is carbonized to form metal carbonate and/or basic metal carbonates.Due to increasing response system pressure, be conducive to
Shorten the carburizing reagent time.Simultaneously for the relatively low ammonia of concentration or carbon dioxide, can pass through to increase response system pressure,
Reaction is promoted quickly to carry out.Thus, it is in order to further speed up response speed or shorten carbonization time, another preferably in the present invention
Embodiment in, in above-mentioned steps S1, control mixed system in the condition that pressure is 0.1～0.95MPa, temperature is 10～95 DEG C
Under continue 0.5～4 hour.The size of precipitation granule of the reaction temperature to preparing, surface electriferous state have an impact, can be according to required
The metal-oxide property of preparation is determining carbonation reaction temperature.Favors low temperature in generate small grain size precipitation granule, high temperature promote from
Son diffusion, the precipitation grain graininess of generation are big, even particle size distribution, and with good solid-liquid separation effect.In said temperature
In the range of disclosure satisfy that the various varigrained diversified demands of various metals carbonic acid salt formation.And the response time by reaction scale,
The factor such as ammonia and flow of carbon dioxide gas amount, pressure affects larger.Reaction scale is big, gas flow is little, pressure is little, then instead
It is long between seasonable；Reaction scale is little, gas flow is big, pressure is big, then the response time is short；Gas stream can be determined according to reaction scale
Amount and pressure, make the response time control at 0.5～4 hour, had both ensured that carburizing reagent was fully carried out, meanwhile, will not be because of the response time
It is oversize to cause gas raw material and energy dissipation.
Metal salt solution including but not limited to alkali metal salt soln, the alkali salt that the above-mentioned preparation method of the present invention is be suitable for is molten
Any one in liquid, transition metal salt solution, gallium saline solution, germanium saline solution, tin-salt solution and antimonic salt solution.It is highly preferred that
Alkali metal salt soln includes sodium salt solution；Alkaline earth metal solution includes calcium salt soln or magnesium salt solution；Transition metal salt solution includes
It is arbitrary in rare earths salt, zirconium salt solution, hafnium saline solution, cobalt salt solution, nickel salt solution, copper salt solution and zinc solution
Kind.The saline solution of these different metals industrially applied range, using value are high, using the preparation method of the present invention, energy
It is enough to prepare that purity is high, the metal-oxide that granularity and morphology controllable, good dispersion, physical property are superior at low cost, and
Preparation process flow process is short, ammonium closed circulation, and cost of material is low, low-carbon environment-friendly.
In the saline solution of above-mentioned metal species, the concrete species of saline solution be chloride solution, nitrate solution, sulfate liquor,
In Acetate Solution and perchlorate solution any one or more.
The present invention above-mentioned preparation method in, carbon dioxide described in step S1 be technical grade carbon dioxide or by
The waste gas recovery of carbon dioxide containing gas is obtained, and the waste gas of the carbon dioxide containing gas is the carbon dioxide gass obtained in step S3
One kind in body and/or metal carbonate precipitate gas, metal carbonate roasting kiln gas, oxalates roasting kiln gas and boiler smoke
Or it is several.
It is raw material that carbon dioxide used by the present invention can be the gas produced from above-mentioned several technical processs, by pressure
Carbon dioxide is obtained after contracting, purification or other process steps, both above-mentioned process gas have been carried out with reasonable utilization, low-carbon emission reduction,
Meet environmental requirement；And and realize effective application of carbon dioxide.Utilize from the Efficient Cycle of cost of material, energy consumption
Angle so that the above-mentioned technique of the present invention becomes the metal-oxide preparation technology of the efficient and low energy consumption that enterprise is really suitable for.
In the same manner, ammonia needed for above-mentioned preparation method is obtained by the recycling of the waste water Jing alkaline matters containing ammonium ion, and contains ammonium
The wastewater source of radical ion can be various, can be the waste water containing ammonium ion, or its produced in above-mentioned steps S1
The waste water containing ammonium ion (including metal extraction separation process and/or carbonate precipitation process) is produced in its industrial process, it is right
In waste water, foreign ion species, content do not limit requirement, are processed and are reclaimed ammonia using above-mentioned recycling step
Realize recycling for ammonia.PH is adjusted using alkaline matter simultaneously, ammonia is extracted by reaction heat and/or external heat, with heat
When the ammonia of amount is used for carburizing reagent, the energy supply in carbonation reaction can be reduced, the energy in whole circulation step is realized
The effectively utilizes of amount, are a kind of low energy consumption, efficient metal-oxide preparation technology, are adapted to enterprise's large-scale application.
In the above-mentioned waste water recycling device step containing ammonium ion, for carrying out the main of the alkaline matter of pH value regulation to waste water
Effect is to adjust the pH containing ammonium ion waste water system so as to generates ammonium hydroxide, by reaction heat and/or external heat, makes hydrogen
Ammonia is escaped in ammonium hydroxide solution.Any alkaline matter that can realize above-mentioned purpose is applied to the present invention.From the reasonable of energy
Using and cost angle consider that above-mentioned alkaline matter can be calcium hydroxide, calcium oxide, magnesium oxide, magnesium hydroxide, light-burned white
One or more in marble, sodium hydroxide, potassium hydroxide.Preferably, alkaline matter be calcium oxide, appointing in sodium hydroxide
It is a kind of.
Alkaline matter is added in waste water containing ammonium ion, with advantages below：First, meeting release reaction heat, this contributes to ammonia
The effusion of gas, can reduce energy resource consumption.Production cost problem, the preferred calcium oxide of alkaline matter or sodium hydroxide is considered simultaneously,
Both alkaline matter low costs, and while a large amount of reaction heat can be released.Second, may contain in the waste water containing ammonium ion miscellaneous
The heavy metal heteroions such as matter metal ion such as Fe, Al, Zn and Cu, by adding alkaline matter regulation system pH value, can
Above-mentioned foreign ion is converted into into precipitation, and is removed by solid-liquid separation；3rd, the ammonia prepared by said method, compared with city
Sell the precipitant such as ammonia and ammonium hydrogen carbonate purity high, be directly used in carburizing reagent, high purity metal oxides product is obtained；
4th, by way of reaction heat and/or external heat escape ammonia, ammonia itself carries uniform temperature, so as to reduce carbon
Change the energy resource consumption in course of reaction.
In above-mentioned steps S3 of the present invention, for different metal carbonates and/or basic metal carbonates, its Roasting Decomposition is
The temperature of oxide is also different；Meanwhile, according to the difference of the Property requirements of the be intended to metal-oxide for preparing, ensureing fully to divide
Under conditions of solving as oxide, can be (air atmosphere, oxygen atmosphere, reducing atmosphere, lazy by adjusting its sintering temperature, atmosphere
Property atmosphere etc.) and roasting time (0.5～12 hour) realizing.Roasting such as to metal-oxide is required by lapse rate, can be led to
Raising sintering temperature is crossed, is extended roasting time and is made fully to be decomposed into metal-oxide, but sintering temperature is too high, roasting time is oversize
Energy consumption can be improved, so as to increase production cost.For the metallic element of variable valency, its calcination atmosphere, such as air gas can be adjusted
Atmosphere, oxygen atmosphere, reducing atmosphere.In air atmosphere, due to the presence for having oxygen, metal can be aoxidized, generate high price gold
Category oxide.
In another kind preferred embodiment of the invention, above-mentioned steps S3 include：By metal carbonate and/or basic metal carbonates
At a high temperature of being placed in 450 DEG C～1100 DEG C, roasting 0.5～12 hour, obtains metal-oxide and carbon dioxide.By roasting
Temperature and time is controlled within the above range, can realize making almost all of metal carbonate and/or basic metal carbonates complete
It is decomposed into metal-oxide.Additionally, the carbon dioxide produced in roasting process, can be returned for carbon by reclaiming, purifying
Change reaction, not only reduce greenhouse gas emission, meet environmental requirement；And realize effective application of carbon dioxide.
Recycle angle and say from cost of material, energy resource consumption, industrial chemicals, be respectively provided with clear superiority so that the above-mentioned work of the present invention
Skill becomes the metal-oxide preparation technology of the efficient and low energy consumption that enterprise is really suitable for.
Beneficial effects of the present invention are further illustrated below in conjunction with specific embodiments.
In the following example, used detection method is as follows：
It is limited using the general analysis all purpose instrument in icp mses, inductive coupling plasma emission spectrograph and Beijing
Responsible company F types atomic absorption spectrophotometer is measured to the constant and trace element of product；
Product granularity is detected using American-European gram of Zhuhai Instrument Ltd. TopSizer America and Europe's gram laser particle size analyzers；
Product surface pattern is measured using HIT's TM3000 scanning electron microscopies.
Product specific surface and aperture, pore volume data adopt the automatic specific surfaces of Kang Ta companies of U.S. Quadrasorb SI-KR/4MP and hole
Footpath distribution detector is measured.
Embodiment 1
Compound concentration is added in precipitation reactor for the solution of cerium chloride by oxidation (absolute purity is 99.5%) of 1.2mol/L, to precipitation
Ammonia to system pH is passed through in reactor and reaches 6～7, be then 1 by ammonia and carbon dioxide gass body mass ratio:1.3 speed are to heavy
Being passed through ammonia and technical grade carbon dioxide (concentration is 99.8%) in the reactor of shallow lake carries out carburizing reagent；In carbonation reaction
Response system is open normal pressure, without the need for external heat, but as the ammonia for participating in reaction carries certain heat, so reaction system
Temperature is 45 DEG C or so, and carburizing reagent continues to obtain cerous carbonate slurry after 2.5h terminates, and carries out filtering, washs and drying obtains carbon
Sour cerium, while reclaim after filtering filter waste liquid, as ammonium chloride waste-water；By the cerous carbonate for drying in 700 DEG C of roastings 2 hours, obtain
To cerium oxide powder, while reclaiming the carbon dioxide that roasting is produced in roasting process.Jing tests the cerium oxide powder purity
99.8%.
Appropriate calcium oxide is added in the waste water of the ammonium chloride of above-mentioned recovery.In course of reaction controlling reaction temperature 88～94 DEG C it
Between, ammonia is persistently escaped and is collected, and this ammonia concentration is 98%, the ammonia recycle is returned and is precipitated for solution of cerium chloride by oxidation.
Embodiment 2
Compound concentration is added in precipitation reactor for the solution of cerium chloride by oxidation of 0.5mol/L, is passed through ammonia to body in precipitation reactor
It is that pH reaches 6～7, is then 1.2 by ammonia and carbon dioxide gass body mass ratio:1 speed be passed through in precipitation reactor ammonia and
Technical grade carbon dioxide (gas concentration lwevel is 99.8%) carries out carburizing reagent；In carbonation reaction, response system is spacious
Mouth normal pressure, without the need for external heat, but as the ammonia for participating in reaction carries certain heat, so temperature of reaction system is 65 DEG C left
The right side, carburizing reagent continue to obtain basic carbonate cerium slurry after 3h terminates, and carry out filtering, wash and drying obtains basic carbonate cerium,
Reclaim after filtering simultaneously and filter waste liquid, as ammonium chloride waste-water；By the cerous carbonate for drying in 700 DEG C of roastings 2 hours, aoxidized
Cerium powder body, while reclaim the carbon dioxide that roasting is produced in roasting process.Jing tests the cerium oxide powder granularity for 3.365 μ
M, particle size distribution (D90-D10)/(2D50) it is 0.98.
Appropriate calcium oxide is added in the waste water of above-mentioned containing ammonium chloride.In course of reaction, controlling reaction temperature is between 68～72 DEG C,
Ammonia is persistently escaped and is collected, and this ammonia concentration is 90%, the ammonia recycle is returned and is precipitated for solution of cerium chloride by oxidation.
Embodiment 3
Compound concentration is added in precipitation reactor for the solution of cerium chloride by oxidation (absolute purity is 99.5%) of 0.5mol/L, to precipitation
Ammonia to system pH is passed through in reactor and reaches 4.5～5.5, be then 1 by ammonia and carbon dioxide gass body mass ratio:2.5 speed to
Being passed through ammonia and technical grade carbon dioxide (gas concentration lwevel is 99.8%) in precipitation reactor carries out carburizing reagent；Carbonization
In course of reaction, response system is open normal pressure, and heating makes temperature of reaction system maintain 95 DEG C or so, and carburizing reagent continues 2h knots
Cerous carbonate slurry is obtained after beam, is carried out filtering, is washed and drying obtains cerous carbonate, while reclaim after filtering that waste liquid is filtered, as
Ammonium chloride waste-water；By the cerous carbonate for drying in 700 DEG C of roastings 2 hours, cerium oxide powder is obtained, while reclaiming roasting in roasting process
Burn the carbon dioxide for producing.Jing SEM are observed, as shown in figure 3, the cerium oxide powder primary particle size is 100-120nm,
There are a large amount of pore passage structures between primary particle and between the second particle reunited of primary particle, Jing tests, its pore volume can
Up to 0.38cc/g, average pore size is 17.89nm, and absolute purity is 99.9%.
Appropriate calcium oxide is added in the waste water of above-mentioned containing ammonium chloride, in course of reaction controlling reaction temperature between 65～75 DEG C, ammonia
Gas is persistently escaped and is collected, and the ammonia recycle is returned and is precipitated for solution of cerium chloride by oxidation.
Embodiment 4
Take appropriate amount of deionized water to be added in precipitation reactor, be passed through ammonia to system pH in precipitation reactor and reach 6～7, so
Afterwards respectively in precipitation system add solution of cerium chloride by oxidation (concentration is 1mol/L), ammonia, carbon dioxide, wherein, ammonia and
Carbon dioxide gass body mass ratio is 1.1:1.In carbonation reaction, response system is open normal pressure, without the need for external heat, but due to
The ammonia for participating in reaction carries certain heat, so temperature of reaction system is 45 DEG C or so, carburizing reagent continues to obtain after 4h terminates
Cerous carbonate slurry, carries out filtering, washs and drying obtains cerous carbonate, while reclaim filtering waste liquid, as ammonium chloride waste-water；Will
This cerous carbonate obtains cerium oxide powder in 700 DEG C of roastings 2 hours.Observed by the cerium carbonate powder pattern to synthesizing, such as
Shown in Fig. 4, the corynebacterium for clustering round is presented, length is 600～800nm, is directly about 300nm or so.As shown in figure 5, roasting
Cerium oxide powder after burning is in relatively decentralized corynebacterium.
Appropriate calcium oxide is added in the waste water of containing ammonium chloride, in course of reaction controlling reaction temperature between 88～94 DEG C, ammonia
Persistently escape and collect, the ammonia recycle is returned and is precipitated for solution of cerium chloride by oxidation.
Embodiment 5
Compound concentration is added in precipitation kettle for the copper chloride solution of 1.5mol/L, in precipitation kettle is passed through ammonia to body
It is that pH reaches 9～10, is then 1.2 by ammonia and carbon dioxide gass body mass ratio:1 speed be passed through in precipitation reactor ammonia and
Carbon dioxide carries out carburizing reagent；In carbonation reaction, response system is normal pressure, and temperature of reaction system is 25 DEG C or so,
Carburizing reagent continues to obtain basic carbonate copper slurry after 3h terminates, and carries out filtering, washs and drying obtains basic copper carbonate, while
Reclaim after filtration and filter waste liquid, as ammonium chloride waste-water；By the basic copper carbonate for drying in 400 DEG C of roastings 5 hours, aoxidized
Copper powder body, while reclaiming the carbon dioxide that roasting is produced in roasting process, is back to copper chloride solution precipitation.
It is 1.782 μm that Jing tests the cupric oxide powder granularity, particle size distribution (D90-D10)/(2D50) it is 0.73, granule is uniform, granularity
Narrow distribution.SEM microscopic appearances are spherical.The cupric oxide powder can be used for the coloring agent of glass, porcelain, and organic conjunction
Into catalyst.
Appropriate sodium hydroxide is added in the waste water of the containing ammonium chloride obtained to said process, and in course of reaction, controlling reaction temperature exists
Between 68～72 DEG C, ammonia is persistently escaped and is collected, and the ammonia recycle is returned and is precipitated for copper chloride solution.
Embodiment 6
Compound concentration is added in precipitation kettle for the zinc nitrate of 2.0mol/L, in precipitation kettle is passed through ammonia to system pH
6.0～6.5 are reached, is then 1 by ammonia and carbon dioxide gass body mass ratio:1 speed is passed through ammonia and dioxy in precipitation reactor
Changing carbon gas carries out carburizing reagent；In carbonation reaction, response system is open normal pressure, and temperature of reaction system is 10 DEG C or so,
Carburizing reagent continues to obtain basic zinc carbonate slurry after 2.5h terminates, and carries out filtering, washs and drying obtains basic zinc carbonate, together
When filter after reclaim and filter waste liquid, as ammonium nitrate wastewater；By the basic zinc carbonate for drying in 400 DEG C of roastings 5 hours, oxygen is obtained
Change zinc powder body, while reclaiming the carbon dioxide that roasting is produced in roasting process, be back to the precipitation of zinc nitrate solution.
It is 0.982 μm that Jing tests the Zinc oxide powder granularity, particle size distribution (D90-D10)/(2D50) be 0.57, can be used for natural rubber,
The vulcanizing activator and reinforcing agent and coloring agent of synthetic rubber and latex.
The above-mentioned pH value containing ammonium nitrate wastewater is adjusted with calcium oxide, solid-liquid separation is carried out as pH=6.0, remove Fe in waste liquid,
The elements such as Al, heavy metal ion, foreign ion clearance are about 99.9%.Continue to add appropriate oxidation in the waste water containing ammonium nitrate
Calcium, in course of reaction, between 65～75 DEG C, ammonia is persistently escaped and is collected controlling reaction temperature, and this ammonia concentration is 99%, will
The ammonia recycle returns the precipitation for zinc nitrate solution.
Embodiment 7
Compound concentration is added in precipitation kettle for the zirconyl chloride solution of 1.5mol/L, adjusts system pH in precipitation kettle
2.0～3.0 are reached, is then 1 by ammonia and carbon dioxide gass body mass ratio:4 speed are passed through ammonia and dioxy in precipitation reactor
Changing carbon gas carries out carburizing reagent；In carbonation reaction, response system is open normal pressure, and temperature of reaction system is 65 DEG C or so,
Carburizing reagent continues to obtain zirconium oxycarbonate slurry after 4h terminates, and carries out filtering, washs and drying obtains zirconium oxycarbonate, while
Reclaim after filtration and filter waste liquid, as ammonium chloride waste-water；By the zirconium oxycarbonate for drying in 1000 DEG C of roastings 4 hours, oxygen is obtained
Change zirconium powder body, while reclaiming the carbon dioxide that roasting is produced in roasting process, be back to the precipitation of zirconyl chloride solution.
It is 99.85% that Jing tests the carburizing reagent yield, and in Emission in Cubic, primary particle size is the Zirconium powder of preparation
100～150nm, particle dispersion are good, as shown in fig. 6, SEM microscopic appearances are spherical, the powder body can be used as zircon ceramic
Raw material.
Appropriate sodium hydroxide is added in the waste water of the containing ammonium chloride produced to said process, controlling reaction temperature exists in course of reaction
Between 90～95 DEG C, ammonia is persistently escaped and is collected, and this ammonia concentration is 95%, the ammonia recycle is returned molten for zirconium oxychloride
The precipitation of liquid.
Embodiment 8
Compound concentration is added in precipitation reactor for the cerous acetate solution of 0.1mol/L, and in adjusting precipitation reactor, system pH reaches
To 5.5～6, it is then 1 by ammonia and carbon dioxide gass body mass ratio:2 speed are passed through ammonia and technical grade two in precipitation reactor
Carbon oxide gas (concentration is 99.8%) carry out carburizing reagent；In carbonation reaction, the pressure of response system is controlled to 0.5MPa,
Temperature of reaction system is made for 70 DEG C or so by external heat, and carburizing reagent continues cerous carbonate slurry to be obtained after 1h terminates, and carries out
Filter, washing and drying obtain cerous carbonate, while reclaim after filtering filtering waste liquid, the as waste water containing ammonium ion, continue to adopt
Above-mentioned steps reclaim ammonia；By the cerous carbonate for drying in 1000 DEG C of roastings 3 hours, cerium oxide powder is obtained, while roasting process
It is middle to reclaim the carbon dioxide that roasting is produced.
It is 3.721 μm that Jing tests the cerium oxide powder granularity, particle size distribution (D90-D10)/(2D50) its shape is observed for 0.83, SEM
Looks belong to petal-shaped (not shown).
The pH value containing ammonium ion waste water that above-mentioned precipitation process is produced is adjusted with calcium oxide, solid-liquid separation is carried out as pH=4.0,
The elements such as Fe, Al, heavy metal ion in removing waste liquid, foreign ion clearance are about 98.5%.Continue to containing ammonium ion
Waste water in add appropriate calcium oxide, be passed through in ammonia evaporation and concentration tower, it is ensured that tower top temperature be 86～93 DEG C, ammonia is persistently escaped,
The ammonia recycle is returned into the precipitation for cerous acetate solution.
Embodiment 9
Compound concentration is added in precipitation kettle for the mixed chlorinated saline solution of cerium zirconium of 1.5mol/L, is passed through in precipitation kettle
Ammonia to system pH reaches 7～8, is then 1.1 by ammonia and carbon dioxide gass body mass ratio:1 speed is led to in precipitation reactor
Entering ammonia and carbon dioxide carries out carburizing reagent；In carbonation reaction, the pressure of response system is controlled to 0.95MPa, passes through
External heat makes temperature of reaction system for 50 DEG C or so, and carburizing reagent continues to obtain cerous carbonate slurry after 0.5h terminates, carry out filtering,
Washing and drying obtain cerium zirconium compound oxide presoma, while reclaim after filtering filtering waste liquid, as ammonium chloride waste-water, continue
Ammonia is reclaimed using above-mentioned steps；By the cerium zirconium compound oxide presoma for drying in 700 DEG C of roastings 3 hours, obtain cerium zirconium and be combined
Oxide powder, while reclaiming the carbon dioxide that roasting is produced in roasting process, is back to the mixed chlorinated salt of cerium zirconium molten
The precipitation of liquid.
Jing test carburizing reagent yields are 99.91%, and the cerium zirconium compound oxide powder body specific surface of preparation reaches 137m2/ g, granularity is
2.659 μm, particle size distribution (D90-D10)/(2D50) it is that 0.76, SEM microscopic appearances are spherical (not shown), meet car tail
The application requirement of gas catalyst aid.
Appropriate calcium oxide is added in the waste water of above-mentioned containing ammonium chloride, is passed through in ammonia evaporation and concentration tower, it is ensured that tower top temperature is
86～93 DEG C, ammonia is persistently escaped, and the ammonia recycle is returned the precipitation for the mixed chlorinated saline solution of cerium zirconium.
Embodiment 10
Solution of cerium chloride by oxidation (absolute purity be 99%) of the compound concentration for 1.2mol/L, starts charging from the upper inlet of tower reactor,
Ammonia and carbon dioxide are passed through from the lower inlet of tower reactor simultaneously, make three carry out carburizing reagent in a counter-current fashion.
Wherein, ammonia and carbon dioxide gass body mass ratio are 1:1.3.In carbonation reaction response system pressure be 0.3MPa, reactant
Be temperature for 18 DEG C, carburizing reagent continues cerous carbonate slurry to be obtained after 4h terminates, carry out filtering, wash and drying obtains cerous carbonate,
Reclaim after filtering simultaneously and filter waste liquid, as ammonium chloride waste-water；By the cerous carbonate for drying in tunnel cave 1100 DEG C of roastings 12 hours,
Cerium oxide powder is obtained, while reclaiming the carbon dioxide that roasting is produced in roasting process, solution of cerium chloride by oxidation is back to
Precipitation.It is 99.2% that Jing tests the cerium oxide powder purity, and carburizing reagent yield is 99.8%.
Calcium oxide is added in the waste water of above-mentioned containing ammonium chloride, appropriate calcium oxide is added, and in course of reaction, controlling reaction temperature exists
Between 88～94 DEG C, ammonia is persistently escaped and is collected, and this ammonia concentration is 90%, and this ammonia is back to the precipitation of solution of cerium chloride by oxidation.
Comparative example 1
Compound concentration is added in precipitation reactor for the solution of cerium chloride by oxidation (absolute purity is 99.5%) of 1.2mol/L, adjusts heavy
In the reactor of shallow lake, system pH reaches 6～7, and being then added thereto to ammonium hydrogen carbonate carries out precipitation；React during precipitation
System is open normal pressure, and temperature of reaction system is 45 DEG C or so, and precipitation continues to obtain cerous carbonate slurry after 2.5h terminates, and enters
Row is filtered, washing and drying obtain cerous carbonate, by the cerous carbonate for drying in 700 DEG C of roastings 2 hours, obtains cerium oxide powder.Jing
The cerium oxide powder purity is tested for 99.1%, impurity F e contents increase in powder body, with increased compared with Fe contents in raw material
237ppm。
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
(1) the purity height of the metal-oxide prepared using the present invention, granularity and morphology controllable, good dispersion, physical property are excellent
More, the special physical property demand that new high-tech material is increasingly improved to metal-oxide can be met.If zirconia-based ceramic material is to Zirconium powder
Possess big primary particle size, cerium zirconium co-catalysis material to cerium zirconium compound oxide high-ratio surface, the requirement of multi-pore channel.
(2) carbon dioxide in metal-oxide preparation process can be recycled, and realize greenhouse gases recycling, reach
The effect of low-carbon emission reduction is arrived.
(3) the ammonia-containing water cycle applications of industry generally existing are effectively reduced ammonia nitrogen discharge, is industry in carbonization precipitation process
Green circulatory development provides thinking.
(4) the features such as present invention has process is simple, industrial chemicals closed circulation utilization, low production cost, is suitable for industrialization
Large-scale production.
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-oxide, it is characterised in that the preparation method includes：
Step S1, carries out precipitation using ammonia and carbon dioxide, and controls the quality of three to metal salt solution
Than making the pH value of mixed system in the range of 2.0～10.0, serosity is obtained；
Step S2, carries out solid-liquid separation to the serosity, obtains the waste liquid containing ammonium ion and metal carbonate and/or gold
Category subcarbonate；And
Step S3, carries out roasting to the metal carbonate and/or basic metal carbonates, obtain the metal-oxide and
The waste gas of carbon dioxide containing gas；
Wherein, the ammonia adjusts stripping enrichment after pH by the waste water containing ammonium ion Jing alkaline matter and obtains.
2. preparation method according to claim 1, it is characterised in that the metal salt solution is individual metal salt solution or various
The mixed solution of metal salt solution.
3. preparation method according to claim 1, it is characterised in that in step S1, the ammonia and carbon dioxide gass
The mass ratio of body is 1.2:1～1:4.
4. preparation method according to claim 1, it is characterised in that the ammonia is obtained as follows：
To in the waste water containing ammonium ion, add the alkaline matter pH to be adjusted to 3.0～6.0, obtain solidliquid mixture；
Solid-liquid separation is carried out to the solidliquid mixture, filtrate is obtained；
The alkaline matter is continuously added in the filtrate, ammonia is obtained；Stripping enrichment is carried out to the ammonia, is obtained
The ammonia.
5. preparation method according to any one of claim 1 to 3, it is characterised in that in step S1, control are described
Mixed system pressure be 0.1～0.95MPa, temperature be 10～95 DEG C under conditions of continue 0.5～4 hour.
6. preparation method according to any one of claim 1 to 3, it is characterised in that in step S1, the metal
Saline solution includes alkali metal salt soln, alkaline-earth metal salt solution, transition metal salt solution, gallium saline solution, germanium saline solution, stannum
Any one in saline solution and antimonic salt solution.
7. preparation method according to claim 6, it is characterised in that the alkali metal salt soln includes sodium salt solution；The alkali
Earth metal solution includes calcium salt soln or magnesium salt solution；The transition metal salt solution include rare earths salt, zirconium salt solution,
Any one in hafnium saline solution, cobalt salt solution, nickel salt solution, copper salt solution and zinc solution.
8. preparation method according to claim 7, it is characterised in that the metal salt solution is that chloride solution, nitrate are molten
In liquid, sulfate liquor, Acetate Solution and perchlorate solution any one or more.
9. preparation method according to any one of claim 1 to 3, it is characterised in that the carbon dioxide is technical grade
Carbon dioxide is obtained by the waste gas recovery of carbon dioxide containing gas, and the waste gas of the carbon dioxide containing gas is step
The carbon dioxide obtained in S3 and/or metal carbonate precipitate gas, metal carbonate roasting kiln gas, oxalates roasting
One or more in kiln gas and boiler smoke.
10. preparation method according to any one of claim 1 to 3, it is characterised in that the waste water containing ammonium ion is industry
The waste water produced in production process, the waste water that the industrial processes are produced include the waste water that metal extraction separation process is produced
And/or the waste water that precipitated metal process is produced；Wherein, the waste water that the precipitated metal process is produced is obtained in including step S2
The waste liquid containing ammonium ion.
11. preparation methoies according to any one of claim 1 to 3, it is characterised in that the alkaline matter be calcium hydroxide,
One or more in calcium oxide, magnesium oxide, magnesium hydroxide, light dolomite, sodium hydroxide and potassium hydroxide, preferably
The alkaline matter is calcium oxide or sodium hydroxide.
12. preparation methoies according to any one of claim 1 to 3, it is characterised in that step S3 includes：
At a high temperature of the metal carbonate and/or basic metal carbonates are placed in 400 DEG C～1100 DEG C, roasting 0.5～12 is little
When, obtain the waste gas of the metal-oxide and the carbon dioxide containing gas.
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| PCT/CN2016/098526 WO2017041738A1 (en) | 2015-09-09 | 2016-09-09 | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide |
| AU2016318839A AU2016318839B2 (en) | 2015-09-09 | 2016-09-09 | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide |
| MYPI2018700514A MY188939A (en) | 2015-09-09 | 2016-09-09 | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide |
| ZA2018/00912A ZA201800912B (en) | 2015-09-09 | 2018-02-12 | Recycling process of wastewater containing ammonium ion and preparation method of metal oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828963A (en) * | 2017-10-31 | 2018-03-23 | 四川英创环保科技有限公司 | A kind of utilization process of rare earth oxide production process carbon dioxide and ammonium |
| CN111170353A (en) * | 2020-02-07 | 2020-05-19 | 包头稀土研究院 | Method for preparing rare earth fluoride by carbon cycle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077753A (en) * | 1992-04-18 | 1993-10-27 | 景治熙 | Active zinc flower and high-purity zinc oxide preparation technology |
| CN102730742A (en) * | 2012-07-09 | 2012-10-17 | 昆山市千灯三废净化有限公司 | Technique for producing soluble copper oxide from acidic etching waste liquor |
| CN103101957A (en) * | 2012-12-21 | 2013-05-15 | 泰兴冶炼厂有限公司 | Method for preparing high-purity low-chlorine electroplating-grade cupric oxide |
| CN103130250A (en) * | 2011-11-22 | 2013-06-05 | 北京化工大学 | Method for preparing active magnesium oxide |
-
2015
- 2015-09-09 CN CN201510572391.9A patent/CN106517294B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077753A (en) * | 1992-04-18 | 1993-10-27 | 景治熙 | Active zinc flower and high-purity zinc oxide preparation technology |
| CN103130250A (en) * | 2011-11-22 | 2013-06-05 | 北京化工大学 | Method for preparing active magnesium oxide |
| CN102730742A (en) * | 2012-07-09 | 2012-10-17 | 昆山市千灯三废净化有限公司 | Technique for producing soluble copper oxide from acidic etching waste liquor |
| CN103101957A (en) * | 2012-12-21 | 2013-05-15 | 泰兴冶炼厂有限公司 | Method for preparing high-purity low-chlorine electroplating-grade cupric oxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828963A (en) * | 2017-10-31 | 2018-03-23 | 四川英创环保科技有限公司 | A kind of utilization process of rare earth oxide production process carbon dioxide and ammonium |
| CN111170353A (en) * | 2020-02-07 | 2020-05-19 | 包头稀土研究院 | Method for preparing rare earth fluoride by carbon cycle |
| CN111170353B (en) * | 2020-02-07 | 2022-10-28 | 包头稀土研究院 | Method for preparing rare earth fluoride by carbon cycle |
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