CN106698509B - Composite Nano zirconium oxide, continuous preparation method and its equipment of even particle size distribution - Google Patents
Composite Nano zirconium oxide, continuous preparation method and its equipment of even particle size distribution Download PDFInfo
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- CN106698509B CN106698509B CN201510788627.2A CN201510788627A CN106698509B CN 106698509 B CN106698509 B CN 106698509B CN 201510788627 A CN201510788627 A CN 201510788627A CN 106698509 B CN106698509 B CN 106698509B
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Abstract
The invention discloses a kind of composite Nano zirconium oxide of even particle size distribution, continuous preparation method and equipment, method is to be carried along into reactor by carrier gas after the precursor of zirconium oxide after evenly mixing and the precursor gasification of stabilizer, it reacts at high temperature with water vapour, and fast decoupled generates composite Nano Zirconium oxide powder at high temperature.Obtained composite Nano zirconium oxide partial size is 5nm-15nm, and bulk density is no more than 0.2g/cm3；Equipment includes feed system, reaction system and product collection system.Not only fine size, density are small for the zirconium oxide prepared using the method for the present invention, but also can exist in the form of an aerosol.Further, present device is overcome using the product collection of multistage post-processing and vent gas treatment and prepares composite Nano zirconia particles in the presence of the technology barrier for being difficult to effectively collect, improved product yield, while solid dust evolution also being avoided to cause air pollution.
Description
Technical field
The present invention relates to a kind of nanoscale metal oxide powder grade preparation technical fields, are a kind of more specifically
Nanoscale metal oxide powder, its continuous preparation method and its equipment.
Background technique
Zirconium oxide has many advantages, such as heat-resisting, wear-resisting and good chemical stability, makes pottery in chemical sensor, high-performance
The fields such as porcelain, catalysis material receive great attention.It is good disconnected that research work in recent years shows that the zirconium oxide of fine grain has
Toughness and superplasticity are split, is one of the research hotspot of current Material Field.Tiny and uniform, with high purity, reunion the is weak powder of granularity
End is the key that obtain high-performance zirconia product.
Zirconium oxide there are three types of phase, i.e. monoclinic phase, tetragonal phase and cubic phase, each have different crystal phase density and
Thermodynamically stable warm area.Under normal conditions, zirconium oxide room temperature to 1170 DEG C be monoclinic phase, 1170-2370 DEG C be tetragonal phase,
2370-2680 DEG C is cubic phase.The density ratio tetragonal phase and cubic phase of monoclinic phase are small.Pure zirconia powder metallurgy is (usually > 1200
DEG C) sintering after during being cooled to room temperature, since high-temperature-phase (generally tetragonal phase) can occur to low-temperature phase (monoclinic phase)
Phase transition, volume changes, and makes device cracking processed, broken, cannot get high intensity device.In order to overcome the limitation, making
Stabilizer, such as yttrium oxide, calcium oxide, magnesia is added in standby zirconia ceramics powder, composite oxide power is formed, by oxygen
Change zirconium to stablize in tetragonal phase, so that it is broken to crack in cooling procedure after roasting.
Nanoscale zirconium powder is mainly produced using liquid phase method at present.Such as commercialized coprecipitation by
Containing alkali co-precipitation is added in zirconates and dopant mixed solution, hydroxide precipitating is obtained, is then filtered, washed, drying and roasting
Obtain solid solution doped zirconia powder.This method is simple and easy, and the easily controllable multicomponent nanocomposite powder of ingredient can be made,
But the powder reunion degree of the product is big, and subsequent sintering step needs to carry out at a higher temperature, not only energy consumption it is high but also
Crystal grain is grown up significantly, and the mechanical property for influencing ceramics in product there are crackle or cavity is made.
In order to control the reunion of powder, liquid phase method is usually covered using organic solvent washing, addition in preparing powder process
It covers agent, supercritical drying, azeotropic distillation, the means such as organic surface active agent be added.Patent document CN1915836A discloses one
The method that kind prepares nano zircite using the precipitation method controls the concentration of zirconium ion by screening agent, to control zirconium oxide
Nucleation process obtains the nanoparticle of epigranular, purity is high.Patent document CN102442699A provides a kind of by organic
The method of object catalyst preparation nano zircite, this method is by the way that pentaerythrite, trihydroxy methyl third are added into zirconium source aqueous solution
Alkane, 2 methyl valeric acid or 2 ethyl hexanoic acid are catalyst, carry out the zirconium oxide that hydro-thermal reaction prepares tetragonal phase.However, these sides
Method not only increases the complexity and cost of process, and the organic matter introduced often generates danger to environment and personnel health
Evil.In contrast, vapor phase method prepares oxide powder and is valued by people due to having the advantages that not easy to reunite.
Vapor phase method produces oxide powder at present, and the SiO of high quality is successfully made2、TiO2、Al2O3Equal nanometer powders,
Products obtained therefrom purity is high, good dispersion, operation are continuous.But since vapor phase method prepares the composite oxides of multicomponent mixture in technique
Control requires height, and the controllability of component is also relatively poor, limits the industrial application of the technology.Although in 1977, Suyama
(3 (4): Ceramurgia Intern. 141) is just described and is aoxidized preparation ZrO by vapor-phase halides2Powder, but this method
Preparation temperature is very high, and it is obvious to there is a problem of that crystal grain is grown up.The gas phase heat that Japan Patent JP61-201604A passes through organic zirconium
Solution or hydrolysis prepare zirconium oxide, but the product that the technology obtains is the porous structure of unformed shape, and contains carbon residue.Patent document
CN1259488A provides a kind of preparation method of the weakly agglomerated nano zircite of surface doping, which passes through ZrCl4Gas
It mutually hydrolyzes and nano zircite is made, stabilizer ions are then introduced by dipping again.The preparation flow is longer, and dipping process
The stabilizer basic load of middle introducing is not stable solid solution in zirconium surface.
Summary of the invention
A kind of even particle size distribution easy to reunite is not allowed in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide
Composite Nano zirconia particles；
It is a further object of the present invention to provide a kind of preparation processes, and it is equal which can be used for preparing above-mentioned size distribution
Even nano zircite, the technique can be with continuous operations, high income；Further, which can also realize production process ring
It protects；
It is yet another object of the invention to provide a kind of equipment, are used especially for above-mentioned technique.
The purpose of the present invention is achieved by the following technical scheme:
A kind of composite Nano zirconium oxide of even particle size distribution, in the composite Nano zirconium oxide zirconia content be 90~
97wt%, stabiliser content are 3~10wt%, and partial size 5nm-15nm, bulk density is no more than 0.2g/cm3；Preferably, institute
Stating zirconium oxide is tetragonal phase, and stabilizer metals oxide enters zirconium oxide crystal phase, i.e. η=0 in the form of solid solution, and η is to stablize
The percentage of the crystal content of agent metal oxide.
Preferably, the average grain diameter of the composite Nano zirconium oxide is 5nm, and bulk density is no more than 0.2g/cm3。
A kind of continuous preparation method of the composite Nano zirconium oxide of even particle size distribution,
Enter reactor after the precursor of zirconium oxide after evenly mixing and the gasification of the precursor of stabilizer, at high temperature with
Water vapour reacts, and fast decoupled generates nano zirconium oxide powder to hydroxide generated at high temperature；
Preferably, the molar ratio of the precursor of the precursor and stabilizer of the zirconium oxide is 1:0.02~0.10；
Preferably, zirconium oxide precursor and the molar ratio of vapor are 1:2.1~3.0；
Preferably, it is carried after the precursor of the zirconium oxide after evenly mixing and the gasification of the precursor of stabilizer by carrier gas
Into reactor.
Preferably, the water vapour is generated by hydrogeneous imflammable gas combustion process；
Preferably, the hydrogeneous imflammable gas refers to the imflammable gas that water is produced after burning, including hydrogen, natural
Gas, oil refinery dry gas, liquefied gas, the alkane of C1-C6, C1-C6 alkene；Preferably hydrogen or methane；
Preferably, the precursor of zirconium oxide refers to the change that zirconium oxide can be produced with steam reaction and after high-temperature roasting
Close object, including zirconium chloride, zirconium-n-propylate, zirconium iso-propoxide；
Preferably, stabilizer is metal oxide, preferably the one or more of yttrium oxide, titanium oxide or magnesia
Combination, more preferably yttrium oxide and/or titanium oxide；
Preferably, the precursor of the titanium oxide is that titanium oxide can be produced with steam reaction and after high-temperature roasting
Compound, the combination including one or more of titanium tetrachloride, butyl titanate or isopropyl titanate, more preferably four
Titanium chloride；
Preferably, the precursor of the yttrium oxide is that yttrium oxide can be produced with steam reaction and after high-temperature roasting
Compound, preferably yttrium isopropoxide, normal propyl alcohol yttrium.
Preferably, the carrier gas is Ar, N2, He or CO2One of or a variety of mixed gas；Preferably Ar and/or
N2。
Preferably, the reaction temperature in the reactor is controlled at 600 DEG C or more, and preferably 650~800 DEG C.
Preferably, the continuous preparation method of the nano zircite of above-mentioned even particle size distribution, specifically comprises the following steps:
1) it is passed through hydrogeneous imflammable gas and air and/or oxygen into reactor, is mixed entering in reactor
Burning generates water vapour；Alternatively, entering reactor in such a way that carrier gas carries water vapour；
2) precursor of uniformly mixed zirconium oxide precursor and the metal oxide as stabilizer is carried using carrier gas
It into reactor, and reacts with aforementioned water vapor and generates hydroxide, fast decoupled generates surely hydroxide at high temperature
Nano zirconium oxide powder after fixed；Preferably, the carrier gas is heated to 650 DEG C or more；
3) air-flow for carrying nano zircite carries out product collection by product collection system；
Preferably, gas is post-processed after product collection system to discharge after meet the requirement of environmental protection.
Preferably, in the step 1), when fuel gas is hydrogen, fuel gas and oxygen or the oxygen in air
Volume ratio is 2:1~1.2；When fuel gas is methane, fuel gas is 1:2 with the volume ratio of oxygen or the oxygen in air
~2.5.
Preferably, in the step 1), when entering reactor by the way of carrying water vapour using carrier gas, into reaction
Mixed gas is heated to 650 DEG C or more before device；
Preferably, steam partial pressure is 1~100KPa, more preferable 10~50kPa；
Preferably, the carrier gas is Ar, N2, He or CO2One or both of or more mixed gas, preferably
Ar and/or N2；
Preferably, in the step 2), the proportionate relationship of the vapour pressure of zirconium oxide precursor and stabilizer precursor is 50:
1~5, more preferable 30:1~1.5.
Further, product separation system is multistep treatment in the step (3), includes at least cyclone separator and gas-solid
Separator two parts use cyclone separator to carry out product collection, then first in the gas containing particulate matter that reactor comes out
It is handled using gas-solid separator, and collects product particle；
Preferably, the gas-solid separator uses bag filter, fiber or ceramic filter；
Preferably, in the step (3), post-processing approach is carried out to gas are as follows: filtered tail gas uses wet dedusting
And/or high-pressure electrostatic precipitation is handled, treated, and gas empties after lye absorbing hydrogen chloride.
A kind of equipment continuously preparing composite Nano zirconium oxide,
It include: feed system, reaction system, product collection system, wherein
The feed system includes two entrances, respectively the predecessor of the precursor of the zirconium oxide of volatile and stabilizer
The entrance of object and the entrance of water vapour；
For the precursor of the precursor and stabilizer of water vapour and zirconium oxide hydrolysis, packet occur for the reaction system
Include reactor, it is preferred that the reactor is externally provided with heating device, for controlling the temperature of reactor.
The equipment of the nano zircite of even particle size distribution of the present invention continuously prepared, particularly may be divided into two types, point
Not as depicted in figs. 1 and 2, the equipment of both types includes following three aspect: feed system, reaction system, product are collected
System.Specifically two types area is illustrated separately below.
Equipment A:
When using hydrogeneous fuel gas and air (and/or oxygen) to burn in reactor top to provide water vapour, use
Three gas circuit apparatuss for feeding.Specifically, the equipment for continuously preparing nano zircite, the feed system includes three gas
Road,
First gas circuit is sequentially communicated by the first air inlet pipe, primary heater and mixer, and carrier gas is from the first air inlet
The air inlet of pipe enters, the precursor of zirconium oxide and the precursor of stabilizer in mixer after evenly mixing, by through first plus
Carrier gas after hot device heating is carried along into reactor head；
Article 2 gas circuit is directly connected to burner noz(zle) by the second air inlet pipe；
Article 3 gas circuit is directly connected to burner noz(zle) by third air inlet pipe；
Second air inlet pipe and third air inlet pipe are respectively used to be passed through hydrogeneous imflammable gas and for being passed through air and/or oxygen
Gas, hydrogeneous imflammable gas enter reactor head after oxidizing fire occurs at burner noz(zle)；
Preferably, flowmeter is equipped at the air inlet of first air inlet pipe, the second air inlet pipe, third air inlet pipe.
Preferably, burner noz(zle) band flame detector, can light a fire immediately when flame surprisingly extinguishes.
Equipment B:
When steam being sent into reactor by the way of carrying vapor using carrier gas, setting for nano zircite is continuously prepared
It is standby, using two-way apparatus for feeding.Specifically, the equipment for continuously preparing nano zircite, the feed system includes two
Gas circuit,
First gas circuit is sequentially communicated by the first air inlet pipe, primary heater and mixer, and carrier gas is from the first air inlet
The air inlet of pipe enters, the precursor of zirconium oxide and the precursor of stabilizer in mixer after evenly mixing, by carrier gas through the
Reactor head is carried along into after the heating of one heater；
Article 2 gas circuit is equipped with the second air inlet pipe and third air inlet pipe, is respectively used to be passed through carrier gas and water, the second air inlet pipe
Converge with third air inlet pipe and converge gas circuit for one and lead to reactor head, secondary heater is provided in Yu Huihe gas circuit, uses
The carrier gas of water vapour is carried in heating；
Preferably, flowmeter is equipped at the air inlet of first air inlet pipe, the second air inlet pipe, third air inlet pipe.
Above no matter which kind of equipment, it is preferred that the product collection system includes cyclone separator and gas-solid separator,
The cyclone separator air inlet is connected with the product deposition portion of reactor by collecting pipe, the top of the cyclone separator
Gas outlet is connected with gas-solid separator air inlet, and product enters under the carrying of carrier gas from collecting pipe after reactor bottom reaction
Cyclone separator, from cyclone separator bottom collection to portioned product, the gas taken out of by cyclone separator top is using gas
Product particle is further collected from gas-solid separator bottom after solid separator；
Preferably, it is equipped with induced draught system after gas-solid separator, discharge tail gas is made to enter purification recovery device.
The invention has the advantages that:
The method of the present invention carries the zirconium oxide and stabilizer metals oxide of uniformly mixed volatile using carrier gas
Precursor and water vapour, which react, generates hydroxide, and fast decoupled generates the nano oxygen after stablizing to hydroxide at high temperature
Change zirconium powder.Water vapour easily generates zirconium hydroxide with volatile zirconates and stabilizer metals reactant salt, which has
Very big reaction equilibrium constant and reaction rate is in thermodynamics of reactions and kinetically to have very much to the preparation of nano zircite
Benefit.The temperature for keeping reactor is more than 600 DEG C, preferably 650~800 DEG C, reacts the hydroxide of generation at such a temperature
Can fast dewatering, formed stabilizer doping after zirconium oxide aerosol.The zirconium oxide nano-particle prepared using this method is few
Reunite, average grain diameter can be no more than 0.2g/cm down to 5nm, bulk density3。
It is small that the zirconium oxide prepared using the method for the present invention not only realizes fine size, density, can be in the form of an aerosol
In the presence of.Meanwhile present device is collected using the product of multistage post-processing and vent gas treatment, overcomes and is preparing nanometer small oxygen by force
Change zirconium particle and there is the technology barrier for being difficult to effectively collect, improve product yield, while solid dust evolution also being avoided to cause
Air pollution.
Have the advantages that partial size is small, uniformity is good, reunion is few using zirconium oxide nano-particle prepared by the present invention, has wide
General application prospect.Since it is with nanometer size effect, sintering temperature is low, tight when craft articles or sintex,
It is not easy to adsorb pollutant dirty and not easy to break；The nano zircite also has good bionical performance, can be used as aoxidizing
The material of zircon ceramic tooth.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of present device 1 (embodiment 1)；
Fig. 2 is the structural schematic diagram of present device 2 (embodiment 2)；
Wherein, the first air inlet pipe of 1-, the second air inlet pipe of 2-, 3- third air inlet pipe, 4- burner noz(zle), 5- reactor, 51- are produced
Object deposition portion, 52- reactor heating device, 6- collecting pipe, 7- cyclone separator, 8- gas-solid separator, 9- induced draught system, 10-
Flowmeter, 11- mixer, 12- primary heater, 13- secondary heater.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1:
A kind of equipment of composite Nano zirconium oxide continuously prepared comprising feed system, reaction system and product are collected
System, wherein the feed system includes two entrances, respectively before the precursor of the zirconium oxide of volatile and stabilizer
The entrance of body object mixture and the entrance of water vapour；The reaction system for water vapour and volatile oxidation zirconium precursor and
Hydrolysis, including reactor occur for the precursor of stabilizer, it is preferred that the reactor is externally provided with heating device, for controlling
The temperature of reactor processed, the product collection system are used to complete to collect the nano zircite product of generation.Wherein, charging system
System at least can be there are two types of embodiment, the first scheme are as follows:
Feed system includes three road gas feeds as shown in Figure 1:, and first gas circuit is by the first air inlet pipe 1, primary heater
12 and mixer 11 be sequentially communicated, carrier gas from the air inlet of the first air inlet pipe 1 enter, it is preferred to use flowmeter 10 accurately control
Make its flow, the precursor of zirconium oxide and stabilizer in mixer 11 after evenly mixing, into pipeline, by through primary heater
Carrier gas after 12 heating is carried along into reactor 5.Imflammable gas and air and/or oxygen containing hydrogen each lead into second into
Tracheae 2 and third air inlet pipe 3 preferably enter reactor through burner noz(zle) 4 after flowmeter 10 respectively.Preferably, burning spray
Mouth band flame detector, can light a fire immediately when flame surprisingly extinguishes.Preferably, mixer is equipped with meter, based on
Measure the precursor of zirconium oxide and stabilizer.
Reaction system: including reactor 5, reactor 5 is made of heat-resisting material, and imflammable gas is sent out at burner noz(zle)
Raw oxidizing fire, and guarantee that the fuel gas in reactor is constantly in combustion state, reaction system is maintained at 600 DEG C or more,
It is preferred that 650~800 DEG C；Easily with the precursor of volatile oxidation zirconium and stabilizer hydrolysis occurs for the water vapour of generation, generates
Doping type zirconium hydroxide can quickly decompose generate zirconium oxide at high temperature, thus in reactor bottom, i.e. reactant
Deposition portion 51 obtains nano zircite product.
Preferably, in order to preferably collect nano zircite product, 5 lower part of reactor is in the cone cell tapered to bottom.
Product collection system: including cyclone separator and gas-solid separator two parts.Due to being obtained out of reaction system
Product average grain diameter be less than 15nm, do not reunite substantially, exist with aerosol shape, apparent bulk density be no more than 0.2g/
cm3, in order to improve product yield, while solid dust evolution also being avoided to cause air pollution, multistage collection can be set.Carrier gas
Product enters cyclone separator 7 from collecting pipe 6 after the reaction of carrying, from 7 bottom collection of cyclone separator to portioned product, by revolving
The product that the gas on 7 top of wind separator is taken out of further collects product particle from bottom using after gas-solid separator 8.
Preferably, in order to preferably collect nano zircite product, cyclone separator 7 and/or 8 lower part of gas-solid separator are in
The cone cell tapered to bottom.
For the transfer efficiency for improving gas, it is preferable that increase induced draught system 9 after gas-solid separator 8.Preferably, it is discharged
Tail gas also needs to discharge after alkali cleaning removes hydrogen chloride, and specifically, tail gas can be by using wet dedusting and/or height
Pressure electrostatic precipitation is handled, and treated, and gas empties after lye absorbing hydrogen chloride.
Nano zircite is prepared by the scheme of the embodiment, low energy consumption, and production is easy, and cost is relatively low, and production obtained
Product even particle size distribution, average grain diameter are not reunited in 5-15nm, and purity is high, for impurity content less than 0.2%, yield is higher,
And good dispersion, it may be implemented continuously to prepare.
Embodiment 2:
A kind of equipment of composite Nano zirconium oxide continuously prepared, the feed system of the present embodiment are not arrange in embodiment 1
Second scheme out, specifically: as shown in Figure 2: feed system by two-way gas feed composition, first gas circuit by first into
Tracheae 1, primary heater 12 and mixer 11 are sequentially communicated, and carrier gas enters from the air inlet of the first air inlet pipe 1, using stream
Meter 10 accurately controls its flow, the precursor of zirconium oxide and stabilizer in mixer 11 after evenly mixing, into pipeline, by
Carrier gas after the heating of primary heater 12 is carried along at the top of reactor 5, in the structure of this gas circuit and the first scheme
Structure is essentially identical；Article 2 gas circuit is equipped with the second air inlet pipe and third air inlet pipe, and carrier gas and water pass through the second air inlet pipe 2 respectively
After converging with third air inlet pipe 3,5 top of reactor is entered after secondary heater 13, this method is by being directly added into water
Steam is completed to react, and reaction and the decomposition reaction of zirconium hydroxide are only hydrolyzed in reactor, and by-product is reduced.Preferably,
Mixer is equipped with meter, for measuring the precursor of zirconium oxide and stabilizer.
Reaction system: reactor 5 is made of heat-resisting material, and outside band heating device 52 makes reaction system be maintained at 600
DEG C or more, preferably 600~800 DEG C；Precursor into the water vapour in reaction system easily with volatile oxidation zirconium and stabilizer
Hydrolysis occurs, the doping type zirconium hydroxide of generation can quickly decompose at high temperature generates zirconium oxide, thus anti-
Device bottom is answered, i.e. product deposition portion 51 obtains nano zircite product.
Product collection system is same as Example 1.
Although the device structure of the embodiment is different from embodiment 1, its nano zirconium oxide powder obtained equally has
Even particle size distribution, average grain diameter are not reunited in 5-15nm, and purity is high, yield is higher, and good dispersion, similarly may be used
To realize continuous preparation, while the scheme of the present embodiment also has control more accurate, and obtained product quality is better
Advantage.
Embodiment 3:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit carries zirconium chloride and different using High Purity Nitrogen
The gas of propyl alcohol yttrium, wherein the vapour pressure of zirconium chloride and yttrium isopropoxide is respectively 30kPa and 1kPa, flow 1.5m3/h.The
The flow of air is 2.5m in two gas circuits3/ h, gas circuit 3 use pentane, flow 1.0m3/h.Article 2 gas circuit and third
Gas circuit enters reactor by casing, and igniter is equipped near mixer outlet, into reactor after n-hexane occur
It burns, the temperature in the reactor is 720 DEG C, and the doping type zirconium hydroxide of generation can quickly decompose at high temperature, raw
At the zirconium oxide after stabilization.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 4nm.The specific surface area (BET) of the product is 172m2/ g, yield 93wt%.
Embodiment 4:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit carries zirconium chloride and different using High Purity Nitrogen
The gas of propyl alcohol yttrium, wherein the vapour pressure of zirconium chloride and yttrium isopropoxide is respectively 30kPa and 1kPa, zirconium chloride and isopropanol
The molar ratio of yttrium is 1:0.02, flow 1.5m3/h.The flow of air is 4.8m in Article 2 gas circuit3/ h, Article 3 gas circuit are adopted
With methane, flow 0.5m3/h.The molar ratio of zirconium chloride and vapor is 1:2.1, steam partial pressure 10KPa, second
Gas circuit and Article 3 gas circuit enter reactor by casing, and igniter is equipped near mixer outlet, into reactor
Hydrogen burns afterwards, and the temperature in the reactor is 650 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 5nm.The specific surface area (BET) of the product is 198m2/ g, yield 92wt%.
Embodiment 5:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit is fed using High Purity Nitrogen and carries zirconium chloride
And the gas of yttrium isopropoxide mixing, wherein the vapour pressure of zirconium chloride and yttrium isopropoxide mixture is respectively 30kPa and 1.5kPa,
The molar ratio of zirconium chloride and yttrium isopropoxide is 1:0.10, flow 1.5m3/h.The flow of air is in Article 2 gas circuit
2.50m3/ h, Article 3 gas circuit use propylene, flow 1.0m3The molar ratio of/h, zirconium chloride and vapor is 1:3.0, water
Partial vapour pressure is 1KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and set near mixer outlet
Have igniter, into reactor after propylene burn, the temperature in the reactor be 720 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 5nm.The specific surface area (BET) of the product is 175m2/ g, yield 93wt%.
Embodiment 6:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit using high-purity argon gas carry zirconium chloride and
The gas of normal propyl alcohol yttrium, wherein the vapour pressure of zirconium chloride and yttrium isopropoxide is respectively 15kPa and 1kPa, zirconium chloride and positive third
The molar ratio of alcohol yttrium is 1:0.06, flow 1.5m3/h.The flow of oxygen is 1.25m in Article 2 gas circuit3/ h, Article 3 gas circuit
Fuel gas be methane, flow 0.5m3The molar ratio of/h, zirconium chloride and vapor is 1:2.5, and steam partial pressure is
50KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and igniter is equipped near mixer outlet,
Hydrogen burns after into reactor, and the temperature in the reactor is 780 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 4nm.The specific surface area (BET) of the product is 138m2/ g, yield 97wt%.
Embodiment 7:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit is carried different using high-purity carbon dioxide gas
The gas of propyl alcohol zirconium and yttrium isopropoxide, wherein the vapour pressure of zirconium iso-propoxide and yttrium isopropoxide is respectively 20kPa and 1kPa, flow are
1.5m3The molar ratio of/h, zirconium iso-propoxide and yttrium isopropoxide is 1:0.8.The flow of air is 2.50m in Article 2 gas circuit3/ h, the
Three gas circuits use liquefied gas, flow 1.0m3The molar ratio of/h, zirconium iso-propoxide and vapor is 1:2.8, steam partial pressure
For 100KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and igniting is equipped near mixer outlet
Device, into reactor after liquefied gas burn, the temperature in the reactor be 720 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 4nm.The specific surface area (BET) of the product is 163m2/ g, yield 92wt%.
Embodiment 8:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit carries zirconium chloride and four using High Purity Nitrogen
The gas of titanium chloride, wherein the vapour pressure of zirconium chloride and titanium tetrachloride is respectively 20kPa and 0.95kPa, flow 2.0m3/
H, the molar ratio of the precursor of the precursor and stabilizer of zirconium oxide are 1:0.03.The flow of oxygen is in Article 2 gas circuit
1.25m3/ h, the fuel gas of Article 3 gas circuit are methane, flow 0.5m3/ h, mole of zirconium oxide precursor and vapor
Than for 1:2.9, steam partial pressure 30KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and are mixing
Device near exit be equipped with igniter, into reactor after methane burn, the temperature in the reactor be 750 DEG C.
Reaction product is white powder, analyzed using dynamic laser light scattering experimental, it is titania-doped after zirconium dioxide
Average grain diameter is 5nm.The specific surface area (BET) of the product is 159m2/ g, yield 96wt%.
Embodiment 9:
Using the nano zircite continuous producing apparatus of Fig. 2, first gas circuit carries zirconium chloride and four using High Purity Nitrogen
The gas of titanium chloride, wherein the vapour pressure of zirconium chloride and titanium tetrachloride is respectively 20kPa and 0.95kPa, flow 2.0m3/
H, the molar ratio of the precursor of the precursor and stabilizer of zirconium oxide are 1:0.05.Article 2 gas circuit is steamed using the water that argon gas carries
Vapour, total flow 2.50m3The molar ratio of/h, zirconium oxide precursor and vapor is 1:2.4, steam partial pressure 42kPa.This
Two-way gas enters reactor after needing to be heated to 600 DEG C, reactor needs further heating to maintain the temperature at 650 DEG C.
Reaction product is white powder, analyzed using dynamic laser light scattering experimental, it is titania-doped after zirconium dioxide
Average grain diameter is 5nm.The specific surface area (BET) of the product is 139m2/ g, yield 94wt%.
Embodiment 10:
Using the nano zircite continuous producing apparatus of Fig. 2, first gas circuit carries zirconium chloride and four using High Purity Nitrogen
The gas of titanium chloride, wherein the vapour pressure of zirconium chloride and titanium tetrachloride is respectively 50kPa and 1kPa, flow 2.0m3/ h, oxygen
The molar ratio for changing the precursor of zirconium and the precursor of stabilizer is 1:0.07.The water vapour that Article 2 gas circuit uses argon gas to carry,
Total flow is 2.50m3The molar ratio of/h, zirconium oxide precursor and vapor is 1:2.6, steam partial pressure 3kPa.This two-way
Gas enters reactor after needing to be heated to 800 DEG C, reactor needs progress heating to maintain the temperature at 800 DEG C.
Reaction product is white powder, analyzed using dynamic laser light scattering experimental, it is titania-doped after zirconium dioxide
Average grain diameter is 3nm.The specific surface area (BET) of the product is 175m2/ g, yield 97wt%.
Embodiment 11:
Using the nano zircite continuous producing apparatus of Fig. 2, first gas circuit carries zirconium chloride and four using High Purity Nitrogen
The gas of titanium chloride, wherein the vapour pressure of zirconium chloride and titanium tetrachloride is respectively 10kPa and 1kPa, flow 2.0m3/ h, oxygen
The molar ratio for changing the precursor of zirconium and the precursor of stabilizer is 1:0.07.The water vapour that Article 2 gas circuit uses argon gas to carry,
Total flow is 2.50m3The molar ratio of/h, zirconium oxide precursor and vapor is 1:2.4, steam partial pressure 50kPa.This two-way
Gas enters reactor after needing to be heated to 700 DEG C, reactor needs progress heating to maintain the temperature at 700 DEG C.
Reaction product is white powder, analyzed using dynamic laser light scattering experimental, it is titania-doped after zirconium dioxide
Average grain diameter is 5nm.The specific surface area (BET) of the product is 198m2/ g, yield 93wt%.
Embodiment 12:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit carries zirconium-n-propylate and titanium using high-purity Ar
The gas of sour four butyl esters, wherein the vapour pressure of zirconium-n-propylate and butyl titanate is respectively 30kPa and 1kPa, flow 1.5m3/
H, the molar ratio of the precursor of the precursor and stabilizer of zirconium oxide are 1:0.05.The flow of air is 2m in Article 2 gas circuit3/
H, gas circuit 3 use natural gas, flow 1.0m3/ h, the precursor of zirconium oxide and the molar ratio of vapor are 1:2.4, and water steams
Gas partial pressure is 30KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and are equipped near mixer outlet
Igniter, into reactor after natural gas burn, the temperature in the reactor be 600 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 10nm.The specific surface area (BET) of the product is 162m2/ g, yield 90wt%.
Embodiment 13:
Using the nano zircite continuous producing apparatus of Fig. 1, first gas circuit carries zirconium-n-propylate and different using high-purity He
The gas of propionic acid titanium, wherein the vapour pressure of zirconium-n-propylate and butyl titanate is respectively 30kPa and 1kPa, flow 1.5m3/ h,
The molar ratio of the precursor of the precursor and stabilizer of zirconium oxide is 1:0.08.The flow of air is 2.2m in Article 2 gas circuit3/
H, gas circuit 3 use oil refinery dry gas, flow 1.0m3/ h, the precursor of zirconium oxide and the molar ratio of vapor are 1:2.8, water
Partial vapour pressure is 25KPa.Article 2 gas circuit and Article 3 gas circuit pass through casing and enter reactor, and set near mixer outlet
Have igniter, into reactor after oil refinery dry gas burn, the temperature in the reactor be 800 DEG C.
Reaction product is white powder, is analyzed using dynamic laser light scattering experimental, and the zirconium dioxide after doped yttrium oxide is put down
Equal partial size is 13nm.The specific surface area (BET) of the product is 169m2/ g, yield 94wt%.
Embodiment 14:
Using the nano zircite continuous producing apparatus of Fig. 2, first gas circuit uses the mixing of High Purity Nitrogen and carbon dioxide
Gas carries the gas of zirconium chloride and titanium tetrachloride, wherein the vapour pressure of zirconium chloride and titanium tetrachloride be respectively 20kPa and
0.95kPa, flow 2.0m3/ h, the molar ratio of the precursor of the precursor and stabilizer of zirconium oxide are 1:0.06.Article 2 gas
The water vapour that road uses carbon dioxide to carry, total flow 2.50m3/ h, the precursor of zirconium oxide and the molar ratio of vapor are
1:2.3, steam partial pressure 42kPa.This two-way gas enters reactor after needing to be heated to 600 DEG C, and reactor is needed into one
Step heating is to maintain the temperature at 680 DEG C.
Reaction product is white powder, analyzed using dynamic laser light scattering experimental, it is titania-doped after zirconium dioxide
Average grain diameter is 15nm.The specific surface area (BET) of the product is 156m2/ g, yield 97wt%.
Comparative example 1:
Using the nano zircite continuous producing apparatus of Fig. 1, the first air inlet pipe 1 carries zirconium chloride using High Purity Nitrogen,
The vapour pressure of middle zirconium chloride is 30kPa, flow 1.5m3/h.The flow of air is 2.5m in second air inlet pipe 23/ h, third
Air inlet pipe 3 uses hydrogen, flow 1.0m3/h.Second air inlet pipe 2 and third air inlet pipe 3 pass through casing and enter reactor, and
Igniter is equipped near mixer outlet, into reactor after hydrogen burn, the temperature in the reactor be 720 DEG C.
Obtain Zirconium oxide powder.
It takes 450 gram of five water yttrium nitrate (analyzing pure, traditional Chinese medicines chemical reagents corporation) to be dissolved in 8 kilograms of deionized waters, is made into nitre
Then sour yttrium aqueous solution is immersed in 3.7 kilograms of above-mentioned zirconium dioxides in the solution.Then heating evaporation solvent while stirring.
After solvent is evaporated, it is put into 110 DEG C of oven drying 10h.Sample B1 is obtained, is analyzed using dynamic laser light scattering experimental, B1's is averaged
Partial size is 20nm, illustrates that oxide particle part is reunited in dipping process.
Comparative example 2:
Using the nano zircite continuous producing apparatus of Fig. 1, the first air inlet pipe 1 carries zirconium chloride gas using High Purity Nitrogen
Body, wherein the vapour pressure of zirconium chloride is 30kPa, flow 1.5m3/h.The flow of air is 4.8m in second air inlet pipe 23/ h,
Third air inlet pipe 3 uses methane, flow 0.5m3/h.Second air inlet pipe 2 and third air inlet pipe 3 pass through casing and enter reaction
Device, and igniter is equipped near mixer outlet, into reactor after hydrogen burn, the temperature in the reactor is
650℃.Obtain Zirconium oxide powder.
Yttrium nitrate is introduced referring to the method dipping of comparative example 1, obtains sample B2.It is analyzed using dynamic laser light scattering experimental, B2
Average grain diameter be 18nm, illustrate that oxide particle part is reunited in dipping process.
Embodiment 15:
In order to further discriminate between the difference between different adsorbents, the crystal phase composition of all samples is analyzed.Crystal phase point
Analysis using X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans,
Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), the Rietveld model (RIQASrietveld that is corrected
Analysis, operation manual, Material Data, Inc., Berkley, CA (1999)), different samples are analyzed, and using quasi-
The method of conjunction calculates the crystal phase composition of sample.Using being equipped with the long fine focusing copper X-ray source of 40kV, 30mA driving
Philips XRG3100 generator；Philips3020 digital goniometer and Philips3710MPD control computer；And Kevex
The cooling silicon detector of PSI Peltier carries out all X-ray diffraction measurements.Using Kevex4601 ion pump controller,
Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A are mono-
Channel analyser operates Kevex detector.
Diffraction pattern is obtained using 4.1c editions softwares of Philips APD.Use Material Data, Inc.
Riqas3.1c editions softwares (Outokumpu HSC Chemistry for Windows: user's manual, Outokumpo
Resarch Oy, Pori, Finland (1999)) carry out all rietveld calculating.
Wherein the crystal phase composition of the sample of embodiment 1-14 only has zirconium oxide, η=0, composite metal ion, that is, stabilizer
Metal ion, enter zirconium oxide crystal phase, i.e. η=0 in the form of amorphous phase, η is that the crystal phase of composite metal ion oxide contains
The percentage of amount.Zirconia content is 95% in sample B1 crystal phase composition, yttrium oxide crystal content is 5%, i.e. η=5；Sample B1
Zirconia content is 95% in crystal phase composition, yttrium oxide crystal content is 5%, i.e. η=5.
In conclusion zirconium oxide nano-particle prepared by the present invention has the advantages that partial size is small, uniformity is good, reunion is few,
It is with a wide range of applications.There is nanometer size effect using the Zirconium oxide nano grain, sintering temperature is low, craft articles
Or tight when sintex, it is dirty and not easy to break that pollutant is not adsorbed；The nano zircite also has bionical well
Performance can be used for the material of zirconia ceramics tooth.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (18)
1. a kind of composite Nano zirconium oxide of even particle size distribution, it is characterised in that: zirconium oxide in the composite Nano zirconium oxide
Content is 90~97wt%, and stabiliser content is 3~10wt%, and partial size 5nm-15nm, bulk density is no more than 0.2g/cm3；
The zirconium oxide is tetragonal phase, and stabilizer metals oxide enters zirconium oxide crystal phase, i.e. η=0 in the form of solid solution, and η is steady
Determine the percentage of the crystal content of agent metal oxide；Wherein, the composite Nano zirconium oxide is prepared by following methods:
Reactor is carried along by carrier gas after the precursor of even mixed zirconium oxide and the gasification of the precursor of stabilizer, at high temperature with
Water vapour reacts, and fast decoupled generates nano zirconium oxide powder to hydroxide generated at high temperature.
2. the composite Nano zirconium oxide of even particle size distribution according to claim 1, it is characterised in that: the composite Nano
The average grain diameter of zirconium oxide is 5nm.
3. a kind of continuous preparation side of such as composite Nano zirconium oxide of the described in any item even particle size distributions of claim 1-2
Method, it is characterised in that: be carried along into after the precursor of zirconium oxide after evenly mixing and the precursor gasification of stabilizer by carrier gas
Reactor reacts with water vapour at high temperature, and fast decoupled generation is nano oxidized at high temperature for hydroxide generated
Zirconium powder.
4. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 3, feature exist
In: the molar ratio of the precursor of the precursor and stabilizer of the zirconium oxide is 1:0.02~0.10；And/or zirconium oxide predecessor
The molar ratio of object and water vapour is 1:2.1~3.0.
5. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 3, feature exist
In: the water vapour is burnt by hydrogeneous imflammable gas to be generated；Wherein, the hydrogeneous imflammable gas produces after referring to burning
The imflammable gas of water, including hydrogen, natural gas, oil refinery dry gas, liquefied gas, the alkane of C1-C6, C1-C6 alkene；
And/or the precursor of zirconium oxide refers to the compound that zirconium oxide can be produced with steam reaction and after high-temperature roasting,
Including zirconium chloride, zirconium-n-propylate or zirconium iso-propoxide；
And/or stabilizer be one or both of metal oxide, including yttrium oxide, titanium oxide, magnesia, calcium oxide and
Above combination；Wherein, the precursor of the titanium oxide is that titanium oxide can be generated with steam reaction and after high-temperature roasting
Compound, the combination including one or both of titanium tetrachloride, butyl titanate or isopropyl titanate or more；The oxidation
The precursor of yttrium is the compound that yttrium oxide can be generated with steam reaction and after high-temperature roasting, including yttrium isopropoxide, just
The combination of one or both of propyl alcohol yttrium；
And/or the carrier gas is Ar, N2, He or CO2One or both of or more mixed gas.
6. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 5, feature exist
In: the water vapour is generated by hydrogen or methyl hydride combustion；And/or the carrier gas is Ar and/or N2。
7. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 3, feature exist
In: the temperature in the reactor is controlled at 600 DEG C or more.
8. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 7, feature exist
In: the temperature in the reactor is controlled at 650~800 DEG C.
9. according to the continuous preparation method of the composite Nano zirconium oxide of the described in any item even particle size distributions of claim 3-8,
It is characterized by: specifically comprising the following steps:
1) it is passed through hydrogeneous imflammable gas and air and/or oxygen into reactor, is mixed and burned and generates in reactor
Water vapour；Alternatively, entering reactor in such a way that carrier gas carries water vapour；
2) precursor that uniformly mixed zirconium oxide precursor and the metal oxide as stabilizer are carried using carrier gas is entered
Reactor, and react with aforementioned water vapor and generate hydroxide, hydroxide at high temperature fast decoupled generate it is stable
Nano zirconium oxide powder；
3) air-flow for carrying nano zircite carries out product collection by product collection system.
10. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 9, feature exist
In: the carrier gas is heated to 650 DEG C or more；
And/or gas is post-processed after product collection system to discharge after meet the requirement of environmental protection；
And/or in the step 1), when imflammable gas is hydrogen, imflammable gas and oxygen or the oxygen in air
Volume ratio is 2:1~1.2；When fuel gas is methane, fuel gas is 1:2 with the volume ratio of oxygen or the oxygen in air
~2.5；
And/or when in the step 1) using reactor is entered by the way of carrier gas carrying water vapour, into reactor before will mix
It closes gas and is heated to 650 DEG C or more；Steam partial pressure is 1~100KPa；
And/or in the step 2), the proportionate relationship of the vapour pressure of zirconium oxide precursor and stabilizer precursor is 50:1~5.
11. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 10, feature
Be: steam partial pressure is 10~50kPa；And/or the proportionate relationship of zirconium oxide precursor and the vapour pressure of stabilizer precursor
For 30:1~1.5.
12. the continuous preparation method of the composite Nano zirconium oxide of even particle size distribution according to claim 9, feature exist
In: product collection system is multistep treatment in the step 3), including cyclone separator processing and gas-solid separator handle two
Point, the gas containing particulate matter that autoreactor comes out uses cyclone separator to carry out product collection first, then using gas-solid
Separator processing, and collect product particle；The gas-solid separator uses bag filter, fiber or ceramic filter；
And/or post-processing approach is carried out to gas are as follows: filtered tail gas using wet dedusting and/or high-pressure electrostatic precipitation into
Row processing, treated, and gas empties after lye absorbing hydrogen chloride.
13. a kind of equipment of continuous preparation such as described in any item composite Nano zirconium oxides of claim 1-2, it is characterised in that:
It include: feed system, reaction system, product collection system, wherein
The feed system includes two entrances, respectively the precursor of the precursor and stabilizer of the zirconium oxide of volatile
The entrance of entrance and water vapour；
Hydrolysis occurs for precursor of the reaction system for the precursor and stabilizer of water vapour and zirconium oxide, including anti-
Device is answered, the reactor is externally provided with heating device, for controlling the temperature of reactor；
The product collection system includes cyclone separator and gas-solid separator, the cyclone separator air inlet and reactor
Product deposition portion is connected by collecting pipe, and the top gas outlet of the cyclone separator is connected with gas-solid separator air inlet,
Product enters cyclone separator from collecting pipe under the carrying of carrier gas after reactor bottom reaction, receives from cyclone separator bottom
Collect portioned product, the gas taken out of by cyclone separator top using after gas-solid separator from gas-solid separator bottom into one
Step collects product particle.
14. the equipment according to claim 13 for continuously preparing composite Nano zirconium oxide, it is characterised in that: the charging system
System includes three gas circuits,
First gas circuit is sequentially communicated by the first air inlet pipe, primary heater and mixer, and carrier gas is from the first air inlet pipe
Air inlet enters, the precursor of zirconium oxide and the precursor of stabilizer in mixer after evenly mixing, by through primary heater
Carrier gas after heating is carried along into reactor head；
Article 2 gas circuit is directly connected to burner noz(zle) by the second air inlet pipe；
Article 3 gas circuit is directly connected to burner noz(zle) by third air inlet pipe；
Second air inlet pipe and third air inlet pipe are respectively used to be passed through hydrogeneous imflammable gas and for being passed through air and/or oxygen,
Hydrogeneous imflammable gas enters reactor head after oxidizing fire occurs at burner noz(zle).
15. it is according to claim 14 continuously prepare composite Nano zirconium oxide equipment, it is characterised in that: described first into
Tracheae, the second air inlet pipe, third air inlet pipe air inlet at be equipped with flowmeter.
16. the equipment according to claim 13 for continuously preparing composite Nano zirconium oxide, it is characterised in that: the charging system
System includes two gas circuits,
First gas circuit is sequentially communicated by the first air inlet pipe, primary heater and mixer, and carrier gas is from the first air inlet pipe
Air inlet enters, the precursor of zirconium oxide and the precursor of stabilizer in mixer after evenly mixing, by through primary heater
Carrier gas after heating is carried along into reactor head；
Article 2 gas circuit is equipped with the second air inlet pipe and third air inlet pipe, is respectively used to be passed through carrier gas and water, the second air inlet pipe and the
Three air inlet pipe, which are converged, to be converged gas circuit for one and leads to reactor head, is provided with secondary heater in Yu Huihe gas circuit, for plus
Heat carries the carrier gas of water vapour.
17. it is according to claim 16 continuously prepare composite Nano zirconium oxide equipment, it is characterised in that: described first into
Tracheae, the second air inlet pipe, third air inlet pipe air inlet at be equipped with flowmeter.
18. the described in any item equipment for continuously preparing composite Nano zirconium oxide of 3-17 according to claim 1, it is characterised in that:
It is equipped with induced draught system after gas-solid separator, discharge tail gas is made to enter reclaiming clean recyclable device.
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| CN101998939A (en) * | 2008-04-09 | 2011-03-30 | 东曹株式会社 | Light-transmitting sintered zirconia compact, process for producing the same, and use thereof |
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