CN1124227A - Technology and equipment for producing ultramicro metallic oxide - Google Patents

Abstract

The present invention uses the ordinary metallic carbonate, oxide, hydroxide, oxalate, and ultramicro carbonate and oxalate etc. as raw material, the nm grade active and ultramicro powder material of metal oxide is obtained by pyrolysis in the device having multiple powerful actions, thus providing high properties raw material featuring large specific surface area, good dispersity, high chemical activity, large scale of production and powerful market competitive capability to the departments of magnetic material, superconductor material and ceramic etc.. The invented technology and apparatus of the precipitation filtration process and the products of ultra micro metallic carbonate and oxalate feature cheap and excellent properties.

Description

Technology that ultramicro metallic oxide is produced and device

The invention belongs to the technical field of industries such as novel material, metallurgy and chemical industry.

" ultra micro " is the abbreviation (calling " UFP " in the following text) of ultrafine particulate (Ultrafine Particles).Ultramicro metallic oxide of the present invention (calling " UFP-∑ MO " in the following text) is meant that metal ∑ M comprises monobasic or polybasic metal at least, as basic metal such as Li, Be.Mg.Ca.Sr, alkaline-earth metal such as Ba, IIA family metals such as Al.Ga.In, Zn, IIB family metals such as Cd, rare earth metals such as Sc, Y, La, IVB such as Ti, Zr family metal, VB family metals such as V, Nb, Ta, group vib metals such as Cr, Mo, W, other metals on filtering metal such as Fe, Co, Ni and the element phase table, ∑ MO are unit or polybasic metal oxide (down with).The superfine material that comprises UFP-∑ MO, contemporary science be it is generally acknowledged can the branch fourth gear: a) micron order (granularity-10～0.1um), b) nano level (granularity :-100～10nm), c) molecular level (granularity-100～20A), atom level (granularity-20A～atom size).UFP of the present invention-∑ O product mainly is meant the powder body material of micron order and nano-grade size size, i.e. the research range of 10～1000nm.

As everyone knows, in the material comminution process, adopt mechanical crushing and grinding equipments such as traditional crusher, ball mill, Raymond machine, to the processing such as materials such as mineral, product granularity reaches-200～325 orders (promptly;-74～45um) is available.But along with the refinement that requires the converted products granularity, the yield rate of the qualified powder of output is just more and more lower, and the consumption of its power and material then can sharply increase, and cost is uneconomical; The jet mill that data [1] is mentioned is that air-flow with subsonic speed or velocity of sound carries powder and processes fine grinding, and the I of granularity reaches 1um, (is not 1m to the maximum but its product purity is high, specific surface area is little ²/ g), granular size inequality, shape irregularity and be with problems such as corner angle, strict demands such as high-purity, the ultra micro that inaccessible modern science and technology develop rapidly proposes powder body material, high reactivity and homogeneity; The preparation method of a class UFP material of artificial acquisition has been pointed out in data [2] and [3], but the details of reparation technology and equipment openly not, and the common issue with of these methods is: 1〉industrial scale is little, by several scales that restrain to feather weight, only is suitable for scientific research; 2〉technical equipment is multiple, and energy consumption is big, is difficult to move towards the industrialization; 3〉use expensive starting material, the production cost height is difficult to widespread use, and product lacks the market competitiveness.In a word, the problem of the economy of these technology of production UFP material is not well solved for a long time.

Task of the present invention is used at least a soluble metal salt ∑ MX (X=SO ₄, (No ₃) ₂, Cl ₂, promptly soluble vitriol, nitrate.Muriate.Down with) or its mixing salt solution, with at least a carbonate MZ (M=Na ₂, NaH, K ₂, basic metal and/or (NH such as KH ₄) ₂, NH ₄H etc. contain NH ₄ ⁺Down with) or the solution effects of its mixing salt and oxalic acid etc., generate metal carbonate precipitation, metal oxalate precipitation and MX salt (MX=vitriol, nitrate, muriate and slightly acidic liquid.Mother liquor down together), and filtering separation acquisition ultra micro metal carbonate (call in the following text " UFP-∑ MCO ₃"), the powder (UFP-∑ MCO of ultra micro metal oxalate (calling " UFP-∑ MA " in the following text) ₃/ ∑ MA calls " UFP-∑ MZ powder " in the following text) do raw material, produce A ∑ MO and UFP-∑ MO with known method for pyrolysis, preferably produce them through pyrolysis master operation such as gather dust, thereby solve an above-mentioned long-term unsolved technology and an economic difficult problem preferably, reclaim by-product MX salt and can significantly reduce production costs again, especially can ton scale operation of measuring.Known method for pyrolysis can be used metallurgical furnaces such as reverberatory furnace, rotary kiln, muffle furnace, preferably adopts the vacuum metallurgy stove of indirect heating, the thermolysis of favourable carbonate or oxalate.

Technical process of the present invention comprises sedimentation and filtration, pyrolysis master operation such as gather dust.Its technology of sedimentation and filtration operation and apparatus features, as shown in Figure 1, with at least two transfusion circuits of forming by heating (as steam, electricity, the heating of coal gas equal energy source) thermoregulated header tank A, regulated valve B, under meter C and duct coupling major equipments such as (not having figure) and known instrument, carry clean liquid of ∑ MX and MZ solution to atomic reactor D respectively, after hybrid reaction, inject steel basin E immediately, filter with filter F (as frame pressure filter, centrifugal filter etc.), obtain the powder of UFP-∑ MZ, heat supply is separated operation and is used.The main technique condition of this operation is: a) material concentration: [metal-salt] 0.50～2.50mol ∑ MX, and [precipitation agent] 0.50～1.50.mol MZ, its consumption are 1.01～1.05 times of theoretical consumption; B) solution temperature: the clean liquid temp t of ∑ MX ₁=room temperature～90 ℃, MZ solution temperature t ₂=room temperature～70 ℃; C) mother liquor MX (that is: vitriol, nitrate, muriate, slightly acidic liquid etc.PH=6.8～7.2 down together), The faster the better for stirring velocity.

The characteristics of atomic reactor D of the present invention, as shown in Figures 1 to 3, it is by a common outlet flowing liquid, at least two overlapping or heavy tube construction formed of cover arranged side by side.As: the D type is the tube construction of two overlapping placements arranged side by side, D ₂To D ₃Type is two tube constructions that Cheng Duogen heavily overlaps.In order to make fully mixing of clean liquid of ∑ MX and ∑ MZ solution, lower end at the atomic reactor common outlet, as shown in Figure 2, install one can shower shower nozzle 1, a rotatable screw-blade 2 preferably is set, its an outer magnetic stirrer 3, magneticsubstance of driven vane parcel of being provided with within it, drive blade and quicken rotation, play a part clean liquid of ∑ MX and the abundant mixing of MZ solution.

According to the processing condition of task of the present invention and sedimentation and filtration operation, its operating features with the clean liquid of ∑ M and the MZ solution of predetermined concentration, is respectively charged among two header tank A as shown in Figures 1 to 3, and heating keeps t respectively thereafter ₁With t ₂Temperature, regulate and control the flow of this two classes solution with regulated valve B and under meter C, to satisfy the requirement of precipitin reaction, the consumption of its precipitation agent MZ is 1.01～1.05 times of theoretical consumption.Carry clean liquid of ∑ MX and MZ solution to atomic reactor respectively with above-mentioned at least two transfusion circuits.This two classes solution with certain temperature, also produce precipitin reaction at once in the mixing of the common outlet place of atomic reactor, perhaps the blade cuts that is rotated when producing precipitin reaction of this mixing solutions is pulverized, numerous apertures 4 on shower nozzle 1 disperse, inject steel basin E immediately with the shower shape, the crystal grain of the UFP that precipitin reaction has just generated-∑ MZ, with drive by agitator, the MX liquid of high speed rotating, the mother liquor (calling " rotation mother liquor " in the following text) of slightly acidic liquid contacts, be sheared pulverizing and make it to have little time to grow up, just be dispersed to the rotation mother liquor and go.The fast more then crystal grain of stirring velocity is thin more.The PH=6.8 of mother liquor MX～7.2 are used filter F filtering separation again, just can obtain UFP-∑ MZ powder, for using by preface down.

∑ MO grain growth may when overcoming pyrolysis, reduce pyrolysis temperature, further crystal grain thinning, increasing specific surface area, solve unsolved for a long time technology and economic headache, the present invention uses the carbonate of the general metal of using always, oxide compound, oxyhydroxide, oxalate, UFP-powders such as ∑ MZ are done raw material, the process characteristic of A ∑ MO and UFP-∑ MO is produced in pyrolysis, as Fig. 4 and shown in Figure 5, comprise the conveying of gas powder at least, pyrolysis, (as: machinery gathers dust to have at least one-level to gather dust, bag collection, electricity gathers dust and waits one of them, and) technological process is (as long and short dash line g down together ₁g ₂g ₃Circuit shown in), preferably include the conveying of gas powder, the preheating of gas powder, pyrolysis, two-stage gather dust final stage for the electricity technological process of gathering dust (as G ₁G ₂G ₃G ₄Circuit shown in).The gather dust main technique condition of operation of pyrolysis is: a) the gas powder is carried---and water content ≯ 10% of ∑ MZ powder contains O ₂The pressure P of gas G ₁=0.50～3.00MPa, it contains O ₂Amount 201～35%, gas powder stream Q=50～200kg/Nm ³B) gas powder preheating---preheating oven fire box temperature t ₁=600～900 ℃, stove tail waste gas outlet temperature t ₂=450～650 ℃; C) pyrolysis temperature t in pyrolysis---the molecule pyrolysis oven furnace pressure 0.01～0.20MPa, stove ₃=300～700 ℃, The faster the better for the rotating speed of diffuser plate, the further refinement of favourable pyrolysis crystal grain.Gathering dust of pyrolytic process has the one-level dust-precipitator at least, the pressure P of the dust-precipitator waste gas outlet of its final stage ₀₂=-1～10mm water column.Preheating oven can be used coal, coal gas, the heating of electric equal energy source, but the electricity consumption of molecule pyrolysis oven, coal gas, coal equal energy source indirect heating, and/or the waste gas indirect heating of preferably using preheating oven to discharge.

According to task of the present invention and the pyrolysis processing condition of master operation such as gather dust, the characteristics of its equipment as shown in Figure 5, the cylinder A that dusts is that (it moves available electronic, power such as electromagnetism moving, pneumatic, mechanical transmission and regulates and control by the regulated valve 2 of powder outlet under the cylinder body 4 of dress ∑ MZ powder, the cylinder body, the powder feeding part 1 that is communicated with valve.Down with) equipment that constitutes of mixing tank 3 component such as grade that are connected with the powder feeding part.Contain O ₂Gas and preferred preheating contain O ₂Gas G, a sends into from mixer entrance, and mix the back with the ∑ MZ powder that the powder feeding part is sent here: b is sent to the molecule pyrolysis oven by its outlet, preferably is sent to the molecule pyrolysis oven after preheating.Flow and the pressure P of regulation and control G ₁Make the gas powder stream Q=50～200kg/Nm of mixing tank output ³Preheating oven is by the body of heater 6 of constructing manufacturing with refractory materials and steel construction etc., has heating member 5 (when using the heating of coal or coal gas, can be installed in an end (burner) of body of heater in the appropriate location of body of heater; As can be installed in when using electrically heated in the body of heater etc., make fire box temperature keep t ₁=600～900 ℃), at the stove tail waste gas outlet 9 is arranged, make its temperature out t ₂=450～650 ℃, at least two group heat-exchanging pieces 7 and 8 are set in body of heater, and (preferably use the heating resisting metal pipe manufacturer, its effect is respectively to containing O ₂The gentle powder stream of gas G Q heating) equipment that waits other parts to constitute.Molecule pyrolysis oven of the present invention is by constructing the body of heater 13 of manufacturing with heating resisting metal materials such as refractory materials and stainless steel or metal titaniums, heating member 10 is arranged on the body of heater, in stove on the furnace wall of an axis both sides correspondence, the diffuser plate 15 of nozzle 11 and rotation is installed respectively, and nozzle is perpendicular to the plate face, diffuser plate preferably directly drives with the outer electric motor of body of heater (not having figure), the progressive dispersion and fining of the fast more favourable more pyrolysis crystal grain of high speed rotating, gentle powder exports the equipment that 12 component such as grade constitute, but electricity consumption, coal gas, coal equal energy source indirect heating body of heater 13 and/or the waste gas residual heat indirect heating of using preheating oven to discharge make temperature t in the stove ₃=300～700 ℃, the pressure P of waste gas outlet ₀₁=-10～10mm water column, regulation and control are injected flow, year powder concentration (kg/Nm of gas powder stream Q in the stove ³) and the interior pyrolytical condition cooperation of stove, make its pressure P ₂=0.01～0.20MFa, ∑ MZ powder is able to the abundant pyrolysis step refining crystal grain of going forward side by side at this.

According to task of the present invention and the pyrolysis processing condition and the equipment characteristic of master operation such as gather dust, the operating features of this operation (being working method and characteristics thereof) is, as Fig. 4 and shown in Figure 5: a) gas powder conveying operations---the by-pass valve control 2 of the cylinder A that will dust closes, and adorns the ∑ MZ powder of water content ≯ 10% in cylinder body 1.With the combination air delivery device (not having figure) and the preferred pressurized air of using of oxygen cylinder and nitrogengas cylinder, earlier containing O ₂Gas G contains { O ₂Amount, flow and pressure P ₁After mixing up, be sent to the inlet a of mixing tank 3 again, again delivery conduit g ₁g ₂g ₃Or G ₁G ₂G ₃G ₄Clean, make it unimpeded, Open valve 2 falls ∑ MZ powder thereafter, quantitatively powder is sent into mixing tank 3 with powder feeding part 1, reaches to carry gas powder stream Q=50～200kg/Nm ³Purpose, by the outlet b be sent to molecule pyrolysis oven C, preferably after preheating oven B preheating, send the molecule pyrolysis oven to carry out pyrolysis.B) preheating oven operation---start the heating member 5 of preheating oven B, make fire box temperature keep t ₁=600～900 ℃, the gas powder in heat-exchanging piece 7 and 8 is flowed Q and contains O ₂Gas G heating, the spent air temperture regulation and control t=of stove tail outlet 9 ₂450～650 ℃.C) molecule pyrolysis furnace operating---start the heating member 10 of molecule pyrolysis oven C, but the waste gas residual heat indirect heating that preheating oven is discharged is preferably introduced in electricity consumption, coal gas, coal equal energy source indirect heating, made that temperature (being the pyrolysis temperature) keeps t in the stove ₃=300～700 ℃, its waste gas outlet pressure P ₁₀=-10～10nn water column.Start electric motor (not having figure) and drive diffuser plate 15 high speed rotating, the dispersion and fining of fast more favourable more powder.Then the gas powder is flowed Q (preferably the gas powder through preheating flows Q) through nozzle 11 vertical high fast direction diffuser plates, regulate and control its flow and contain powder concentration kg/Nm ³) and with stove in the pyrolytical condition cooperation, make furnace pressure P ₂=0.01～0.20MPa.Powder after the pyrolysis enters dust collecting system from exporting 12.D) operation of gathering dust---have the one-level dust-precipitator at least, as machinery gather dust, known equipment instrument such as bag collection, electricity gather dust, its final stage is gathered dust and with dust precipitator the gas powder is separated, and obtains A ∑ MO, UFP-∑ MO product, the pressure P of its final stage (dust precipitator) waste gas outlet ₀₁=-10～10mm water column.Gather dust technology and the device of operation of pyrolysis of the present invention produced continuously.When blow-on, molecule pyrolysis oven and preheating oven should be at first started, the operation that the gas powder is carried can be carried out thereafter; Before blowing out, should the winding-up of the powder in the containers such as pipeline and heat-exchanging piece 7 and 8 is clean, do not stay trash, the blowing out of just stopping the supple of gas or steam at last.

Contain O ₂Gas G delivers to mixing tank 3 after heat-exchanging piece 8 heating, as shown in Figure 5, form gas powder stream Q and carry out thermal exchange with ∑ MZ powder, is sent to heat-exchanging piece 7 heating once more, makes intensifications of absorbing heat once more of ∑ MZ powder, is injected in the molecule pyrolysis oven by nozzle 11 high speeds.As seen, in the course of conveying of gas powder stream (as G ₁G ₂G ₃G ₄Shown in), powder at first can dewater, and part powder (as the carbonate of metal, oxyhydroxide, oxalate etc., the temperature that its theoretical pyrolysis begins is all below 300 ℃) beginning pyrolysis is also arranged, in pressure P ₁Under the effect of=0.50～3.00MPa, by the atwirl diffuser plate of the high fast direction of nozzle.Powder will be subjected in the molecule pyrolysis oven: a) speed that penetrates from nozzle of gas powder stream Q is up to subsonic speed, velocity of sound, even supersonic speed direct projection diffuser plate, produces the jet crush force, helps the powder particulate and advances to go on foot one by one refinement; B) diffuser plate of high speed rotating, the gas powder stream Q to perpendicular to the plate face produces powerful mechanical shear stress, obtains the same good effect with (a); C) when high pressure gas powder stream Q injected in the stove, pressure was by P ₁=0.50～3.00MPa falls sharply to P suddenly ₃=0.01～0.20MPa produces the expansion diffusive force at once, effect with " popcorn effect ", make the inside of ∑ MZ powder particulate be created in observed under the electron microscope " crackle " and " groove " (size of having only nm～A), thereby improved specific surface area significantly.Adopt known vacuum metallurgy stove to handle ∑ MZ powder, the effect that also can produce popcorn effect.

In sum, under the condition of molecule pyrolysis oven of the present invention, effect when ∑ MZ powder is subjected to the powerful strength of three kinds of jet crush force, mechanical shear stress, expansion diffusive forces etc., not only refinement crystal grain, refinement crystal grain can significantly reduce pyrolysis temperature again, but also produce " popcorn effect " best effect, thereby greatly improved the specific surface area of A ∑ MO and UFP-∑ MO product, granularity refinement reaches nanometer (nm) grade.

Accompanying drawing is described in detail as follows:

Fig. 1 is the technology and device synoptic diagram of sedimentation and filtration, comprises and can heat thermoregulated header tank A, regulated valve B, under meter C, atomic reactor D (D wherein ₁Type is the tube construction of two overlapping placements), steel basin E, pressure filter F etc.t ₁With t ₂Be respectively the temperature of clean liquid of ∑ MDX and MZ solution.

Fig. 2 is that the atomic reactor structural representation of band shower nozzle comprises: D ₂The type atomic reactor is two heavily tube constructions of cover, interior pipe and the solution of carrying ∑ MX and MZ respectively, shower nozzle 1, rotating paddle 2, magnetic stirrer 3, numerous aperture 4.

Fig. 3 is the front view and the vertical view of each model of atomic reactor, comprising: D ₃Type is two heavily tube constructions of cover, and two fluid inlets are arranged on the outer tube, can carry two kinds of different solution; D ₄Type is two and tubulation bigger tube construction of overcoat again, D ₅Type is in the four-way pipe one has two fluid inlets on the tube construction of one in overcoat and the overcoat pipe again, and all the other are a fluid inlet.

Fig. 4 is the process schematic representation of the dissatisfied operation of gathering dust of heat.

Fig. 5 is the device synoptic diagram of the dissatisfied operation of gathering dust of heat, comprising: dust cylinder A and powder feeding part 1 thereof, control valve 2, mixing tank 3 and import a and outlet b, cylinder body 4 etc.; Preheating oven B and heating member 5 bodies of heater 6 thereof, heat-exchanging piece 7 and 8, waste gas outlet 9; Molecule pyrolysis oven C and heating member 10 thereof, nozzle 11, gas powder outlet 12, body of heater 13, waste gas outlet 14 etc.; Dust-precipitator D and two-stage dust-precipitator 16 and 17 etc.Long and short dash line g ₁g ₂g ₃Expression contains O ₂Gas G carries the route without the gas powder stream Q of preheating, G ₁G ₂G ₃G ₄The route of representing preheating.P ₀₁Be preheating oven waste gas outlet pressure, P ₀₂Be pyrolysis oven waste gas outlet pressure.

The equipment instrument that the sedimentation and filtration operation is used---rise beaker with two 5 cubes and make header tank, electric furnace pan heating temperature control.For the laboratory with small-sized flow 10～500ml/min scope.Embodiment 1 and the atomic reactor that embodiment 3 to 30 uses are to be with shower nozzle, and having only embodiment 2 is atomic reactors of not being with shower nozzle, and chooses D2 to D5 type, as shown in Figures 1 to 3; Atomic reactor inner tube diameter 1.00mm, outer tube diameter 3.10～6.00mm, adapting pipe (plastic material) internal diameter 3.00～4.00mm.(change scooter 0～2000r/min), place 6 liter beakers to do steel basin with adjustable speed 60W electric mixer.Vacuum pump and 15 liter filter flask filtering separation UFP-ZnCO ₃Other, as thermometer, stopwatch, PH precision test paper etc., it is commonly used to be the laboratory.

Pyrolysis equipment instrument---cylinder cylinder body volume 100 liters that dust that operation is used that gather dust can be made pyrolysis oven by thermoregulated muffle furnace with 5KW, and each is grown 10 meters stainless steel tubes and makes two groups of heat-exchanging pieces with φ 12 * 1.0mm, heats respectively to contain O ₂Gas G and powder stream Q.Form air feed row (calling " gas row " in the following text) with oxygen cylinder and each one of nitrogengas cylinder, regulation and control contain O ₂Gas G contains { O ₂Amount, pressure P 1 and flow.Do the heating member of molecule pyrolysis oven with the temperature automatically controlled muffle furnace of 6KW, the body of heater (useful volume is 400 liters) that indirect thermal is made of stainless steel.Component such as stove is chewed, diffuser plate are all made of stainless steel, and corresponding known tensimeter and thermocouple etc. are installed.Drive the rotating speed of the moving control of single-phase electricity diffuser plate with varitran regulation and control, contain the pyrolysis of Zn powder after, use double-deck bag collection, obtain AZO and UFP-AZO, sampling analysis claims.

The chemical reagent that embodiment acted on is all bought from market, and the analytical test of sample is conventional analysis and surveys detecting method, UFP-ZnCO ₃, powder such as UFP-AZO, use the S of Hitachi, Ltd-570 type scanning electronic microscope to measure.The specific surface area of various powders all uses BET method (being the gas absorption method) to measure.

Embodiment 1:

Use the D2 type atomic reactor of band shower nozzle,, get clean liquid of the 0.51molZnSO for preparing and 0.51ml Na as Fig. 1 and shown in Figure 2 ₂CO ₃Solution is filled respectively in two 5 liter beakers, the clean liquid temp t of ZnSO ₁=room temperature makes Na with electric furnace pan ₂CO ₃Solution keeps t ₂=50～70 ℃, the flow of two kinds of solution of regulation and control is respectively 100ml/min and 101ml/min, deliver to the interior pipe and the outer tube of atomic reactor D2 type respectively, mix in interior pipe exit, produce precipitin reaction at once, injecting stirring velocity immediately is the 6 liter beakers of 250～350r/min, charging reaction 20min, Na ₂SO mother liquor PH=6.9～7.0, filtering separation UFP-ZnCO ₃Powder: powder is moisture 6.8%, the heavy 126.71g of heating under vacuum dehydration back wall, mean particle size (calling " granularity " in the following text) 9.90 μ m, purity (doing) 99.81%ZnCO ₃, calculating the Zn direct yield is 99.26%, test conditions and result thereof list table 1 in.

Embodiment 2

This example is used not with the D4 type atomic reactor of shower nozzle, as Fig. 1 and shown in Figure 3, carries ZnSO, ZnCl respectively with three transfusion circuits ₂With K ₂CO ₃Solution is to two interior Guan Yuyi root outer tubes of atomic reactor, and its working method and process are with embodiment 1, and test conditions and result thereof list table 1 in.

Embodiment 3

This example as Fig. 1 and shown in Figure 3, is respectively carried ZnSO and NaHCO with three transfusion circuits with the D3 type atomic reactor of band shower nozzle ₃, NHHCO ₃Solution is to interior pipe and the outer tube of D3, and working method is the same with embodiment 1 with process, and test conditions and result thereof list table 1 in.

Embodiment 4

With the D5 type atomic reactor of band shower nozzle, Fig. 1 and shown in Figure 5 carries ZnSO, ZnCl respectively with five transfusion circuits ₂, Zn (NO ₃) ₂With Na ₂CO ₃, (NF) ₂CO ₃Solution is to interior pipe and the outer tube of D5, and working method is the same with embodiment 1 with process, and test conditions and result thereof list table 1 in.

Embodiment 5

The atomic reactor D2 of effect band shower nozzle is as Fig. 1 and shown in Figure 2, in advance with 0.86molZnSO and 0.40Znl ₂Fill behind the equal-volume mixing in the header tank (5 liter beaker), use two transfusion circuits to carry ZnSO and ZnCl respectively ₂Mixing solutions with (NH) ₂CO ₃Solution is delivered to the interior pipe and the outer tube of atomic reactor D2 type, and other working method are the same with embodiment 1 with process, and test conditions and result thereof list table 1 in.

Embodiment 6

Get embodiment 5 gained UFP-ZnCO ₃Powder 100.00g (moisture 6.6%, granularity 0.30 μ m, purity (doing) 99.79%ZnCO ₃Spread out on porcelain dish, put into the 5kw muffle furnace in 700 ℃ of following pyrolysis 55min, cooling take out the heavy 54.51g of UFP-AZO product, moisture 1.50%, granularity 1.01 μ m, specific surface area 88.6m ²/ g, purity (doing) 99.75%ZnO, the Zn direct yield that is gathered dust by calculate heat is 99.85%.

Embodiment 7

The present embodiment pyrolysis is gathered dust and is adopted the technology and the device of the conveying of gas powder, pyrolysis, bag collection, shown in Fig. 5 long and short dash line g1g2g3, makes UFP-ZnSO with the processing condition of embodiment 3 to 5 ₃Mixed powder 10.00kg (moisture 9.12%, granularity 0.55 μ m, purity (doing) 99.81%ZnCO ₃Pack into and dust in the cylinder, 6kw molecule pyrolysis oven is warming up to 500～600 ℃.Tease and ridicule control by gas and contain O ₂The pressure P 1=2.35 of gas～3.00NPa, air quantity 0.000Nm ³/ min is sent to the inlet a that the cylinder that dusts mixes device, and opening the following powder speed of control valve 2 controls is 0.200kg/min, through mixing tank output 50kg/Nm ³Gas powder stream, by diffuser plate (the rotating speed 950r/min of duct coupling by nozzle 11 direct projections rotation, the pyrolysis oven internal pressure keeps P2=0.15～0.20MPa, descends the whole powders of powder 50min pyrolysis continuously, blows 8min thereafter again, with remove in the pipeline with the molecule pyrolysis oven in residue, use double-deck bag collection, obtain the heavy 5.33kg of UFP-AZO product, moisture after testing 2.12%, granularity 0.12 μ m, specific surface 120.2m ³/ g, purity (doing) 99.78%ZnO, the Zn direct yield that is gathered dust by a little calculating pyrolysis is 99.81%.

Embodiment 8

Present embodiment uses the gas powder to carry, and the technology and the device of the preheating of gas powder, pyrolysis, bag collection shown in Fig. 5 G1G2G3G4 delivery conduit, are used the UFP-ZnCO of the processing condition gained of embodiment 1 and 2 ₃Powder 10.00kg (moisture 7.81%, granularity 8.95 μ m, purity (doing) 99.83%ZnCO ₃Pack in the spray cylinder, the muffle furnace of 5kw preheating is warming up to 600～850 ℃, the 6kw muffle furnace makes 300～400 ℃ of molecule pyrolysis ovens.Tease and ridicule control with gas and contain { O ₂The amount be 21% (being equivalent to air) pressure P 1=0.55～0.70MPa flow 0.00625m ³The gas of/min exchanges the mixing tank that is sent to the cylinder that dusts after part heats through preheating oven, and it is 0.625kg/min that control valve makes down powder speed, and then gas powder stream is 100kg/Nm ³, the heat-exchanging piece of another in preheating oven heating again by the diffuser plate (rotating speed 1450r/min) of nozzle direct projection rotation, and keeps the molecule pyrolysis oven by pressure P 2=0.01～0.10MPa.Continuously down the whole powders of powder 16min pyrolysis blow 10mim thereafter again to remove the residue in each container, get UFP-AZO product weight 5.45kg with double-deck bag collection, check and analysis: moisture 2.12%, and granularity 0.016 μ m, specific surface area 216m ²/ g, purity (doing) 99.80%ZnO receives this calculating Zn direct yield 99.82% test conditions and result thereof and lists table 2 in.

Embodiment 8b, 9 to 11

Embodiment 8b, 9 to 11 uses powders such as general zinc carbonate commonly used, zinc oxide, zinc hydroxide, zinc oxalate to do raw material, operational path that is adopted and device thereof, working method and process respectively.With embodiment 8 is the same, and test conditions and result thereof list table 2 in.

Embodiment 12 to 30

This crowd of embodiment 12 to 30 is with soluble metal salt clean liquid of ∑ MX and carbonate MZO ₃Solution is done raw material, adopts similarly to Example 1 technology and device, as Fig. 1 and shown in Figure 2, produces metal carbonate ∑ MCO ₃The working method of particulate is the same with process and embodiment 1.The common conditions of embodiment 12 to 20 is: [soluble metal salt] clean liquid 1.45mol ∑ MX, flow 50ml/min, preheating temperature t1=70～90 ℃; (NH) ₂CO ₃Make precipitation agent, 1.45mon, flow 51ml/min, preheating temperature t2=60～70 ℃.Reinforced time 20min, mother liquor stirring velocity 900～1000r/minPH=6.8～7.2 etc., test-results is listed table 2 in.Embodiment 21 and 22 removes (NH) ₂CO ₃Outside the flow 77ml/min difference of solution, all with embodiment 12, the result lists table 2 in to other conditions.Embodiment 23 to 27 removes (NH) ₂CO ₃Outside the solution flow 153ml/min difference, all with embodiment 12, example is gone into table 3 to other conditions as a result.Embodiment 28 to 30 removes (NH) ₂CO ₃Outside the solution flow 102ml/min difference, all with embodiment 12, example is gone into table 3 to other conditions as a result.

Embodiment 31 to 40

This crowd of embodiment 31 to 40.Do raw material with the basic metal of metal ∑ M and the carbonate of alkaline-earth metal and the powders such as oxyhydroxide of metal ∑ M, produce the active metal oxide particulate, its technology that adopts, device, working method and process thereof are the same with embodiment 8, the common conditions of test is: powder weight in wet base 20.00kg contains O ₂Gaseous tension P1=1.50～2.00MPa, flow 0.01Nm ³/ min contains { O ₂20～25%, 750～900 ℃ of preheating temperatures, the following powder speed 1.600kg/mim that the gas powder is carried, following powder time 12.5min, gas powder stream 160kg/Nm ³, temperature is 6000～700 ℃ in the molecule pyrolysis oven, pressure 0.01～0.10MPa, and diffuser plate rotating speed 1800～2000r/min, test-results is listed in the table 4.

41 to 50 crowdes of embodiment 41 to 50 of embodiment are with other ∑s MCO except that basic metal and alkaline earth metal carbonate ₃Carbonate powder is done raw material, except that molecule pyrolysis furnace temperature is reduced to 300～400 ℃.The situation that other pyrolysis are gathered dust is all just the same with embodiment 31, and test-results is listed table 5 in.

Embodiment 51 to 68

This crowd of embodiment 51 to 68 does raw material with powders such as the oxide compound of metal ∑ M and oxalate, removes molecule pyrolysis furnace temperature and reduces to 300～400 ℃, contains { O ₂Outside 21～30%, the situation that other pyrolysis are gathered dust is all just the same with embodiment 31, test-results is listed table 6 in.

Embodiment 69

Chinese patent [4] discloses the ferritic production method of a kind of Mn-Zn.Technology of the present invention and device can be used for producing the magneticsubstance of this quasi-metal oxides, promptly do raw material with the solution of ∑ MX and MZ, make UFP-∑ MCO earlier ₃/ ∑ MA, UFP-∑ MO powder body material is produced in pyrolysis thereafter, and compacting sintering becomes desired geometrical shape then.This example is for producing mol than being Fe ₂O ₃: MnO: ZnO=52.6: 35.4: 12.0 Mn-Zn ferrite.Take for this reason:

Sedimentation and filtration operation: get equal-volume Fe ₂(SO ₄) ₃, MnSO ₄, ZnSO ₄Concentration is respectively the in advance abundant mixing of solution of (mol) 0.526,0.354,0.120, fills in 5 liters of beakers, and the electric furnace pan heating keeps t ₁=80 ℃; Again 1.250molNH ₄HCO solution is filled in another 5 liter beaker, and the electric furnace heating keeps t ₂=65 ℃, use two transfusion circuits (as shown in Figure 1), respectively with the flow volume delivery of 100 and 201 (ml/min) to D ₂The interior pipe and the outer tube of type atomic reactor, be total to charging reaction 20min, inject belt stirrer 6 liter beakers immediately, rotating speed～800r/min, sedimentation and filtration separates mother liquor (PH=7.0), obtains carbonate weight in wet base 173.92g, oven dry back constant weight 161.75g under 100～108 ℃ of rough vacuum, so moisture is 7.00%, sampling analysis contains (%): Fe 36.48Mn 12.08, Zb 4.87, then metal ∑ M yield is 99.93 granularity 45mn.

The pyrolytic process that operation: embodiment 69 to 73 is gathered dust in pyrolysis all carries out in temperature automatically controlled cabinet-type electric furnace (5kw), and with vacuum pump keep the required vacuum tightness of test (-Pa).This example is got above-mentioned powder dry weight 100.00g, shakeouts and sends on porcelain dish in the stove, at t ₃=600 ℃, pyrolysis 20～60min takes out under vacuum tightness-5000Pa, and the sampling check and analysis contain %:Fe 55.40, Mn18.34, Zn 7.40, O ₂18.86, the granularity 16nm 53.65g that weighs, the carefully and all active high composition of 99.51% ∑ M of metal oxide purity yield, 99.90% this powder particles is even etc., is used to prepare Mn-Zn ferrite magnetic conductance and can reaches 4500～6000, and the finished product rate improves 5～10%.Above test-results is listed table 7 in.

Embodiment 70

Chinese patent [5] proposes a kind of method for preparing high temperature superconducting materia.Adopt technology of the present invention and device to be used to make this class superconducting material and will obtain better effect.Sedimentation and filtration process using D ₆Atomic reactor (as Fig. 3) uses three transfusion circuits 0.325molBi (NO ₃) 3+0.200molSr (No ₃) ₂Mixed solution and 0.100molCaCl ₂+ 0.200molCuCl ₂Mixed solution is imported pipe in two of this reactions, 0.988mol H ₂C ₂O ₄(solution input outer tube injects steel basin (6 liters of beakers) immediately after the hybrid reaction, the operation of other operations and pyrolytic process is the same with embodiment 69, and test conditions and result thereof list in the table 7.

Embodiment 71 to 73

Chinese patent [6] has been announced a kind of production technique of stupalith metal oxide.Use technology of the present invention and device, can obtain high quality, low cost, this quasi-metal oxides product on a large scale, test operation and process thereof are the same with embodiment 69, and test conditions and result thereof list table 7 in.

The subordinate list explanation

The condition and the result of table l, EXAMPLE l to 5 sedimentation and filtration;

Condition and result that table 2, embodiment 8 to 11 pyrolysis are gathered dust;

Table 3, the filtering test-results of embodiment 12 to 30 solvable ∑ MX metal salt precipitate;

The test-results that table 4, embodiment 31 to 41 ∑ MZ powder pyrolysis are gathered dust;

Table 5, embodiment 42 to 50 ∑ MCO ₃The test-results that the powder pyrolysis is gathered dust;

The test-results that table 6, embodiment 51 to 68 ∑ MZ powder pyrolysis are gathered dust;

Table 7, embodiment 69 to 73 produce magneticsubstance, superconducting material and stupalith

Deng test-results

The main reference data

1, Duan Xixiang, ore fine grinding and technology characteristics research thereof, Yunnan metallurgy,

1987.6.21～25

2, Hong Guangyan etc., ultra-micro powder synthetic and using, Journal of Inorganic Materials,

1987.697—104

3, Zhang Jiaji etc., ultramicron (UFP) research and use present situation, metallic substance research,

1986.4.41—52

4, Cheng Guzhe etc., the method for producing Mn-Zn ferrite, Chinese patent, application number:

91110692.8, open day: 1992.5.27

5, J Bock etc., high-temperature superconductor and preparation method, Chinese patent application number:

92108768.3, open day: 1993.4.7

6, H irrigates victory etc., the production technique of blended metal oxide powder, Chinese patent Shen

Please number: 91111445.9 open days: 1992.6.24

Table 1

Embodiment	The clean industry of ZnX zinc salt				??????????????[MCO 3] precipitant solution				Reinforced time min	The MX mother liquor
													The title molecular formula	Concentration mo1	Flow ml/min	Temperature t 1, ℃	The title molecular formula	Concentration mol	Flow ml/min	Temperature t 2, ℃	The title molecular formula	The PH value	Stir r/min
	?1 ?2 ?3 ?4 ?5	?ZnSO 4?ZnSO 4?ZnCl 2?ZnSO 4?ZnSO 4?ZnCl 2?Zn(NO 3) 2?ZnSO 4+ZnCl 2	????0.51 ????1.12 ????1.12 ????1.26 ????1.02 ????0.80 ????0.42 ????0.86 ????0.40	????100 ?????25 ?????25 ?????50 ?????50 ?????50 ?????50 ?????50 ?????50	Temperature temperature 70～90 70～90 40～60 60～70 60～70 60～70 50～60 50～60	?Na 2CO 3?K 2CO 3?NaHC 3?NK 4HCO 3?Na 2CO 3(NH 4) 2CO 3?NH 4HCO 3	???0.51 ???1.12 ???1.26 ???1.26 ???1.12 ???1.12 ???1.26	????101 ????105 ????52 ????52 ????51 ????51 ????206		50～70 room temperature 40～60 40～60 50～60 50～60 40～50	?20 ?20 ?20 ?20 ?10 ?10 ?10	?Na 2SO 4?K 2SO 4?Na 2SO 4+(NH 4) 2SO 4MX salt (NH 4) 2SO 4?+NH 4Cl												?6.9～7.0 ?7.0～7.2 ?7.1～7.2 ?6.8～7.1 ?7.0～7.2	?250～350 ?400～600 ?800～1000 ?900～1000 ?900～1000

Embodiment	The carbonization result
						??????????ZnCO 3Measure and the moisture % dry weight g purity % of chemical examination			Zn directly gets rate, %	Mean particle size, um
	?1 ?2 ?3 ?4 ?5	????6.8 ????8.6 ????9.4 ???10.0 ????7.8	?126.71 ?279.92 ?156.84 ?279.13 ?157.16	?99.81 ?99.80 ?99.81 ?99.82 ?99.79	?99.26 ?99.86 ?99.46 ?99.56 ?99.68						????9.90 ????8.00 ????0.60 ????0.40 ????0.30

Table 2

Embodiment	The pyrolysis powder					Contain { O 2Amount %	Flow Nm 3/min	Pressure P 1 MPa
									Title	Weight in wet base kg	Moisture %	Granularity μ m	Purity (doing) %
	????8 ????8b ????9 ????10 ????11	????UFP—ZnCO 3Zinc carbonate zinc oxide zinc hydroxide zinc oxalate	????10.00 ????10.00 ????20.00 ????20.00 ????10.00	????7.81 ????9.56 ????5.56 ????2.12 ????8.21	????8.95 ??????45 ??????43 ??????74 ??????35									?ZnCO 3????99.83 ?ZnCO 3????99.56 ?Zn(OH) 2??95.63 ?ZnO???????99.85 ?ZnC 2O????99.89	????21 ????21 ????26 ????21 ????35	????0.0625 ????0.0625 ????0.008 ????0.010 ????0.010	????0.55～0.70 ????0.55～0.70 ????2.55～3.00 ????2.55～3.00 ????1.50～2.00

Table 2 (continuing)

Embodiment	The gas powder is carried			Preheating oven	The molecule pyrolysis oven		The thermal decomposition test result
														Speed kg/min	Time min	Gas powder stream Q kg/Nn 3	Temperature t 1, ℃	Temperature t 3, ℃	Pressure P 2 MPa	The heavy kg of temperature	Moisture %	Granularity nm	Specific surface area m 2/g	Purity (doing) %	Direct yield %
	????0.625 ????0.625 ????1.600 ????1.600 ????0.800	????16 ????16 ????12.5 ????12.5 ????12.5	????100.00 ????100.00 ????200.00 ????160.00 ?????80.00	????600—850 ????600—850 ????500—600 ????500—600 ????700—850	300—400 300—400 400—500 400—500 600—700	0.01—0.10 0.01—0.10 0.10—0.20 0.10—0.20 0.01—0.15	?????5.41 ?????5.21 ????19.97 ????16.02 ?????5.30	????2.12 ????2.15 ????1.56 ????1.48 ????2.02	???16 ???24 ??140 ??150 ???18	????216 ????140 ?????90 ?????95 ????208	?99.80 ?99.50 ?99.80 ?99.50 ?99.84	?99.82 ?99.85 ?99.81 ?99.80 ?99.82

Annotate: molecule pyrolysis oven diffuser plate rotating speed is 1440～1450r/min, and following powder blows 8-10min after finishing again, to remove residue.

Embodiment 8,8b, 11 products are UFP-AZO, and embodiment 9 and 10 product are AZO.

Table 3

Embodiment	?????1.45mol∑MX		????????????????????????????∑MCO 3The test-results of particulate
									Title	Purity %	Moisture %	Granularity μ m	Title	Dry weight g	Purity %	Direct yield %
	?12 ?13 ?14 ?15 ?16 ?17 ?18 ?19 ?20	?Li 2SO 4?SrCl 2?BaCl 2?Pb(NO 3) 2?CuSO 4?CdSO 4?MnSO 4?FeSO 4?NiSO 4	?95.81 ?98.46 ?98.35 ?99.88 ?99.85 ?98.43 ?98.85 ?98.16 ?98.19	?7.60 ?8.91 ?8.46 ?7.83 ?8.92 ?7.37 ?5.67 ?7.81 ?6.59	?1.24 ?0.12 ?0.13 ?1.32 ?0.34 ?0.62 ?0.16 ?0.11 ?0.12	?Li 2CO 3?SrCO 3?BaCO 3?PbCO 3?CuCO 3?CdCO 3?NnCO 3?FeCO 3?NiCO 3	?115.48 ?233.83 ?311.21 ?418.23 ?195.91 ?268.53 ?176.50 ?181.91 ?183.68	?95.78 ?98.41 ?98.31 ?99.85 ?99.80 ?98.40 ?98.81 ?98.11 ?98.16									?99.56 ?99.45 ?99.52 ?99.46 ?99.55 ?99.46 ?99.85 ?99.78 ?99.65
?21 ?22									?AlCl 3?LaCl 3	?99.58 ?99.99	?9.33 ?8.76	?0.15 ?0.10	?Al 2(CO 3) 3?La 2(CO 3) 3	?186.26 ?363.08	?99.55 ?99.95	?99.53 ?99.76
	?23 ?24 ?25 ?26 ?27	?Bi 2(SO 4) 3?Y 2(SO 4) 3?Ga 2(SO 4) 3?V 2(SO 4) 3?Cr 2(SO 4) 3	?98.46 ?99.98 ?99.55 ?98.42 ?98.33	?8.25 ?8.81 ?9.06 ?9.22 ?8.91	?0.36 ?0.15 ?1.03 ?0.87 ?0.96	?Bi 2(CO 3) 3?Y 2(CO 3) 3?Ga 2(CO 3) 3?V 2(CO 3) 3?Cr 2(CO 3) 3	?940.52 ?567.76 ?508.11 ?452.11 ?450.05	?98.42 ?99.95 ?99.50 ?98.36 ?98.30									?99.48 ?99.75 ?99.70 ?99.68 ?99.51
?28 ?29 ?30									?SiCl 4?TiCl 4?ZrCl 4	?99.85 ?98.35 ?98.51	?9.51 ?9.16 ?9.06	?0.10 ?0.15 ?0.12	?Si(CO 3) 2?Ti(CO 3) 2?Zr(CO 3) 2	?236.56 ?267.13 ?335.64	?99.80 ?98.30 ?98.44	?99.63 ?99.72 ?99.58

Table 4

Embodiment	The 20g wet mash				Active metal oxide	Test-results
												Title	Moisture %	Granularity μ m	(purity) (doing) %	Weight in wet base kg	Moisture %	Granularity nm	Specific surface area (m 2/g)	Purity (doing) %	Direct yield %
	?31 ?32 ?33	?Li 2CO 3?SrCO 3?BaCO 3	?7.60 ?8.80 ?8.42	?1.24 ?0.12 ?0.13		?99.83 ?98.41 ?98.31	?Li 2O ?SrO ?BaO	??7.604 ??13.002 ??14.398	?2.15 ?1.86 ?1.52	?32 ?11 ?8	?228 ?246 ?253											?99.80 ?98.36 ?98.26	?99.54 ?99.62 ?99.58
?34 ?35 ?36 ?37 ?38 ?39 ?40					?Ga(OH) 3?Al(OH) 3?Si(OH) 4?Bi(OH) 3?Nd(OH) 3?Ta(OH) 5?Co(OH) 2							?5.65 ?6.72 ?4.68 ?7.26 ?6.35 ?2.12 ?3.86	??43 ??39 ??35 ??42 ??38 ??40 ??43	?98.62 ?99.56 ?98.72 ?98.69 ?99.85 ?98.67 ?98.78	?Ga 2O 3?Al 2O 3?SiO 2?Bi 2O 3?Nd 2O 3?Ta 2O 5?Co 2O 3	??14.877 ??12.301 ??12.091 ??16.742 ??16.338 ??16.394 ??14.663	?1.88 ?1.03 ?1.66 ?1.01 ?1.36 ?1.05 ?1.36	?138 ?42 ?65 ?126 ?134 ?108 ?115	?205 ?278 ?412 ?201 ?207 ?216 ?208	?98.58 ?99.51 ?98.67 ?98.63 ?99.80 ?98.62 ?98.72	?99.63 ?99.81 ?99.72 ?99.66 ?99.82 ?99.71 ?99.68

Table 5

Embodiment	???????????20kg∑CO 3Wet mash				Active metal oxide	Test-results
												Title	Moisture %	Granularity μ m	Purity (doing) %	Weight in wet base kg	Moisture %	Granularity nm	Specific surface area (m 2/g)	Purity (doing) %	Direct yield %
	?41 ?42 ?43 ?44 ?45 ?46 ?47 ?48 ?49 ?50	?In 2(CO 3) 3?PbCO 3?CuCO 3?Y 2(CO 3) 3?Ti(CO 3) 2?V 2(CO 3) 3?Cr 2(CO 3) 3?MnCO 3?FeCO 3?NiCO 3	?6.66 ?7.83 ?8.92 ?8.81 ?9.16 ?8.86 ?8.91 ?5.67 ?7.81 ?6.59	??45 ?1.32 ?0.34 ?0.15 ?0.15 ?0.87 ?0.96 ?0.16 ?0.11 ?0.12		?98.56 ?99.57 ?99.88 ?99.89 ?98.66 ?98.61 ?98.63 ?98.85 ?98.57 ?98.68	?In 2O 3?PbO ?CuO ?Y 2O 3?TiO 2?V 2O 5?Cr 2O 3?MnO 2?Fe 2O 3?NiO	?12.879 ?15.641 ?11.952 ?11.725 ?8.789 ?11.925 ?9.905 ?14.490 ?12.879 ?11.926	?2.16 ?1.87 ?2.03 ?1.98 ?2.02 ?1.75 ?1.86 ?1.67 ?1.58 ?1.68	?30 ?20 ?18 ?10 ?11 ?21 ?22 ?8 ?6 ?8	????236 ????245 ????250 ????278 ????266 ????248 ????227 ????270 ????280 ????275											?98.52 ?99.51 ?99.82 ?99.83 ?98.61 ?98.58 ?98.58 ?98.80 ?98.52 ?98.62	?99.56 ?99.62 ?99.78 ?99.80 ?99.57 ?99.60 ?99.66 ?99.80 ?99.70 ?99.68

Table 6

Embodiment	The 20kg wet mash				Active metal oxide	Test-results
												Title	Moisture %	Granularity μ m	Purity (doing) %	Humidity kg	Moisture %	Granularity nm	Specific surface area m 2/g	Purity (doing) %	Direct yield %
	?51 ?52 ?53 ?54 ?55 ?56 ?57 ?58 ?59	????CaO ????MgO ????SnO 2????Sb 2O 3????Bi 2O 3????Ag 2O ????Sc 2O 3????Gd 2O 3????Nb 2O 5	????4.68 ????5.72 ????7.75 ????6.45 ????6.88 ????4.72 ????8.35 ????8.36 ????8.27	????45 ????46 ????40 ????41 ????48 ????15 ????35 ????20 ????18		????98.56 ????98.65 ????98.71 ????99.55 ????99.56 ????99.58 ????99.96 ????99.95 ????98.57	??CaO ??MgO ??SnO 2??Sb 2O 3??Bi 2O 3??Ag 2O 2??Sc 2O 3??Gd 2O 3??Nb 2O 5	????18.981 ????18.812 ????18.668 ????19.016 ????18.868 ????19.191 ????18.631 ????18.635 ????18.596	????1.02 ????1.12 ????1.58 ????1.68 ????1.65 ????1.14 ????2.01 ????2.00 ????1.76	????135 ????134 ????131 ????110 ????138 ?????88 ?????96 ?????82 ?????78	????206 ????206 ????207 ????210 ????205 ????221 ????218 ????220 ????230											?99.51 ?99.60 ?98.65 ?99.50 ?99.52 ?99.53 ?99.92 ?99.91 ?98.53	?99.50 ?99.60 ?99.52 ?99.55 ?99.60 ?99.51 ?99.56 ?99.60 ?99.54
?60 ?61 ?62 ?63 ?64 ?65 ?66 ?67 ?68					MoO 3Ge(C 2aO 4) 2Ag 2C 2O 4La 2(C 2O 4) 3Eu 2(C 2O 4) 2Sm 2(C 2O 4) 3Zr(C 2O) 4W(C 2O 4) 3Te(C 2O 4) 2							????6.28 ????6.56 ????5.84 ????7.85 ????7.68 ????7.77 ????8.29 ????8.18 ????7.26	????16 ????1.26 ????1.48 ????1.85 ????1.78 ????1.76 ????2.35 ????2.86 ????2.68	????98.62 ????99.78 ????99.58 ????99.96 ????99.95 ????99.55 ????98.52 ????98.61 ????98.66	??MoO 3??GeO 2??Ag 2O ??La 2O 3??Eu 2O 3??Sm 2O 3??ZrO 2??WO 3??TeO 2	????18.900 ????7.949 ????14.53 ????11.763 ????12.129 ????12.050 ????8.562 ????10.194 ????10.408	????1.67 ????1.55 ????1.56 ????1.78 ????1.87 ????1.66 ????1.68 ????1.92 ????1.57	?????78 ?????21 ?????22 ?????23 ?????23 ?????24 ?????30 ?????31 ?????30	????231 ????246 ????245 ????246 ????245 ????242 ????238 ????238 ????239	?98.58 ?99.73 ?99.55 ?99.92 ?99.91 ?99.51 ?98.48 ?98.56 ?98.62	?99.53 ?99.50 ?99.55 ?99.60 ?99.60 ?99.58 ?99.50 ?99.50 ?99.50

Table 7

Implementation column	Raw material ∑ MX salt scavenging solution			The precipitation agent molecular formula	MZ solution			Reinforced time min	?MX	Mother liquor
											Title molecular formula and concentration mol thereof	Flow ml/min	Temperature t ℃	Concentration mol	Flow ml/min	Temperature t ℃	PH value	Stir r/min
	?69 ?70 ?71 ?72 ?73	?Fe(SO)?0.526，MnSO??0.354 ?ZnSO???0.120 ?Bi(NO)?0.325，Sr(NO)0.200 ?CaCl???0.100??CuCl??0.200 ?BaCl???0.555，CaCl??0.050 ?ZrCl???0.110，TiCl??0.500 ?SrCl???0.500，TeCl??0.500 ?Pb(NO)?0.600，Sn(NO)0.600	???100 ????50 ????50 ???100 ???100 ???100		????80 ????85 ????85 ????80 ????75 ????85	????NHCO ????HCO ??(NH)CO ??(NH)CO ??(NH)CO	?1.250 ?0.988 ?0.913 ?0.750 ?0.750		?201 ?101 ?201 ?201 ?201	??65 ??70 ??65 ??60 ??55									?20 ?20 ?20 ?20 ?20	?7.0 ?6.8 ?7.2 ?7.0 ?7.0	～800 ～950 ～10000 ～1000 ～1000

Sedimentation and filtration UFP-∑ MCO 3/∑∑MA
					Moisture %	Dry weight g	Purity %	Yield %	Granularity nm
????7.00	?161.75	????99.50	?99.93	????45
					????8.60	?189.18	????99.92	?99.95	????41
????9.20	?141.72	????99.68	?99.90	????30
					????8.50	?198.41	????99.51	?99.91	????36
????7.60	?304.75	????99.52	?99.93	????35

Table 7 (continuing)

Embodiment	Powder pyrolytical condition and test-results
											Title	Dry weight g	Temperature t ℃	Vacuum tightness P-Pa	Time min	Net weight g	Granularity nm	Specific surface area m/g	Purity (doing) %	Yield %
	69 70 71 72 73	∑MCO 3∑MA ∑MCO 3∑MCO 3∑MCO 3	100.00 100.00 100.00 100.00 100.00	????600 ????650 ????350 ????700 ????400	?5×10 ?6×10 ?4×10 ?450 ?3×10	?40 ?30 ?55 ?20 ?60	?53.65 ?54.03 ?50.74 ?54.68 ?64.68	????16 ????17 ????19 ????26 ????15	????202 ????201 ????190 ????160 ????216	?99.51 ?99.90 ?99.65 ?99.50 ?99.52											?99.90 ?99.91 ?99.90 ?99.92 ?99.92

Annotate: UFP-∑ MO sample chemical composition (wt%), embodiment (#) is 69 ^#: Fe 55.40, and Mn 18.34, and Zn 7.40, O ₂18.86;

70 ^#：Bi?58.85，Sr?15.18，Ca?3.47，Cu?11.01?O ₂?11.50；71 ^#：Ba?53.90，Ca?1.42，Zr

7.10，Ti?16.94，O ₂?20.64；72 ^#：Sr?33.29，Te?48.48，O ₂?18.23?73 ^#：Pb?55.43，

Sn 31.73, O ₂12.84 embodiment: 69# belongs to Fe ₂MnZnO ₅The type magneticsubstance; 70# belongs to Bi 3.25 SrCa Cu _zO _x

Type superconducting materials such as (X=7.9～8.5); 71# belongs to Ba 1.11 Ca 0.10 Cu 0.20 Ti 3.05 types: 72# belongs to SrTeO ₃

Type, 73#PbSnO ₃Stupaliths such as type.

Claims (10)

1, (metal ∑ M comprises monobasic or polybasic metal at least to use soluble metal salt ∑ MX, as basic metal such as Li, alkaline-earth metal such as Be, Mg, Ca, Sr, Ba, IIIA family metals such as Al, Ga, In, IIB such as Zn, Cd family metal, rare earth metals such as Sc, Y, La, IVB such as Ti, Zr family metal, VB family metals such as V, Nb, Ta, group vib metals such as Cr, Mo, W, other metals on the filtering metals such as Fe, Co, Ni and the periodic table of elements, ∑ MX is at least a salt or its mixing salt in its soluble vitriol, nitrate, the muriate.Together following) and MZ precipitation agent (M=Na ₂, NaH, k ₂, basic metal and/or (NH such as KH ₄) 2, NH ₄H etc. contain NH ₄ ⁺And H ₂ ⁺, promptly MZ makes precipitation agent and also available oxalic acid for its carbonate and makes precipitation agent.Effect down together), produce the technology of active metal oxide (calling " A ∑ MO " in the following text) and ultramicro metallic oxide (calling " UFP-∑ MO " in the following text), comprise sedimentation and filtration, pyrolysis master operation such as gather dust, be characterized in: the sedimentation and filtration operation use at least a solvable ∑ MX or its mixing salt cleansing soln (call in the following text " clean liquid "), with the solution effects of at least a MZ or its blended MZ precipitation agent, generate the ultra micro metal carbonate and (call " UFP-∑ MCO in the following text ₃") or the powder of ultra micro metal oxalate (calling " UFP-∑ MA " in the following text) do raw material, adopt known method for pyrolysis to produce A ∑ MO and UFP-∑ MO, preferably produce A ∑ MO and UFP-∑ MO through pyrolysis master operation such as gather dust.

2, according to claim 1, the main technique condition of sedimentation and filtration operation is: a) material concentration: [metal-salt] 0.50～2.50mol ∑ MX, and [precipitation agent] 0.50～1.50mol MZ, its consumption are 1.01～1.05 times of theoretical consumption; B) solution temperature: the clean liquid temp t of ∑ MX ₁=room temperature～90 ℃, MZ solution temperature t ₂=room temperature～70 ℃; C) mother liquor MX (is vitriol, nitrate, muriate, slightly acidic liquid etc.PH=6.8～7.2 down together), The faster the better for its stirring velocity.

3, its technology of sedimentation and filtration operation of the present invention and apparatus features, take into account the transfusion circuit that equipment such as duct coupling and known instrument are formed by heating temperature adjustment header tank, regulated valve, flow with at least two, carry clean liquid of ∑ MX and MZ solution to atomic reactor respectively, inject in the steel basin immediately through hybrid reaction, with filter filtering separation MX mother liquor, just can obtain UFP-∑ MCO ₃/ ∑ MA powder.(calling " UFP-∑ MZ powder " in the following text)

4, according to claim 1 to 3, the characteristics of atomic reactor, it is by a common outlet flowing liquid, at least two overlapping or heavy tube construction formed of cover arranged side by side, preferably in the lower end of atomic reactor outlet, adorn one can shower shower nozzle, and a screw-blade that drives with magnetic stirrer is set in shower nozzle preferably.

5, according to claim 1 to 4, produce the equipment of A ∑ MO and UFP-∑ MO with known method pyrolysis UFP-∑ MZ powder, can be metallurgical furnaces such as reverberatory furnace, rotary kiln, preferably adopt the vacuum metallurgy stove of indirect heating.

6, the present invention uses carbonate, oxide compound, oxyhydroxide, the oxalate of the general metal of using always, and UFP-∑ MZ powder does raw material, and the process characteristic that A ∑ MO and UFP-∑ MO are produced in pyrolysis is: comprise at least the conveying of gas powder, pyrolysis, at least one-level gather dust (as machinery gather dust, its a kind of such as bag collection, electricity gather dust.Down with), preferably include conveyings of gas powder, the preheating of gas powder, pyrolysis, have the two-stage final stage of gathering dust to be the pyrolysis of electric process such as the gather dust technology of gathering dust.

7, according to claim 1 to 6, the gather dust main technique condition of operation of pyrolysis is: a) the gas powder is carried: water content ≯ 10 of UFP-∑ MZ powder contain O ₂Pressure 0.50～the 3.00MPa of gas, it contains { O ₂Amount 20～35, gas powder stream 50～200kg/Nm ³B) gas powder preheating: 600～900 ℃ of preheating oven fire box temperatures, 450～650 ℃ of stove tail waste gas outlet temperature; C) pyrolysis: pyrolysis temperature is 300～700 ℃ in the molecule pyrolysis furnace pressure 0.01～0.20MPa, stove, and The faster the better for the rotating speed of diffuser plate.

8, the pyrolysis of the present invention device characteristic that master operation produces A ∑ MO and UFP-∑ MO such as gather dust is, at least comprise by the cylinder that dusts, molecule pyrolysis oven, have the one-level dust-precipitator at least, preferably including the cylinder that dusts, preheating oven, dividing in pyrolysis oven, the two-stage final stage of gathering dust is the device that equipment instrument such as dust precipitator and duct coupling are formed.

9, according to claim 8, the characteristics of molecule pyrolysis oven are by constructing the body of heater of manufacturing with refractory materials and heating resisting metal material (materials such as preferred stainless steel, metal titanium), heating member is arranged indirectly to the stove internal heating on the body of heater, in stove on the furnace wall of an axis both sides correspondence, the diffuser plate of nozzle and rotation is installed respectively, nozzle is perpendicular to the plate face, diffuser plate preferably directly drive with the outer electric motor of stove and body of heater on the component such as outlet of powder and the equipment of known instrument formation.

10, according to claim 8 and 9, the characteristics of preheating oven are by the body of heater of constructing manufacturing with refractory materials and steel construction piece etc., there is heating member appropriate location at body of heater, indirect heating is arranged at least two group heat-exchanging pieces (preferably using the heating resisting metal pipe manufacturer) in the stove, the equipment that the stove tail has component such as waste gas outlet and known instrument to constitute.

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