CN112853488B - Equipment and method for preparing tetrapod-like zinc oxide whisker by modified montmorillonite catalyst - Google Patents
Equipment and method for preparing tetrapod-like zinc oxide whisker by modified montmorillonite catalyst Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 99
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 51
- 239000011701 zinc Substances 0.000 claims description 45
- 229910052725 zinc Inorganic materials 0.000 claims description 45
- 229910000278 bentonite Inorganic materials 0.000 claims description 34
- 239000000440 bentonite Substances 0.000 claims description 34
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 34
- 239000013078 crystal Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 238000011027 product recovery Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000013014 purified material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000005192 partition Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 235000000405 Pinus densiflora Nutrition 0.000 description 3
- 240000008670 Pinus densiflora Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001455273 Tetrapoda Species 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000003030 smectite-group mineral Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- -1 wear resistance Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses equipment and a method for preparing tetrapod-like zinc oxide whiskers by using a modified montmorillonite catalyst, which comprise a reaction furnace, air pressure adjusting equipment, a recovery device, a stirring device and a control system, wherein the air pressure adjusting equipment, the recovery device, the stirring device and the control system are respectively connected with the reaction furnace; the reactor comprises a partition plate horizontally arranged in the middle of the reactor, the partition plate divides the reactor into a raw material bin and a catalyst bin from top to bottom, a plurality of through connecting holes are formed in the partition plate, and independent heaters are arranged in the catalyst bin and the raw material bin and are electrically connected with a control system. The four-needle zinc oxide whisker prepared by adopting the technical scheme of the invention has high needle formation rate and good whisker growth, is uniform and regular four-needle whisker, and has uniform whisker size; the furnace pressure and the bin pressure are intelligently controlled; the production cost is low.
Description
Technical Field
The invention relates to the technical field of preparation of tetrapod-like zinc oxide whiskers, in particular to equipment and a method for preparing the tetrapod-like zinc oxide whiskers by using a modified montmorillonite catalyst.
Background
The four-needle zinc oxide whisker (T-ZnOw) is a self-activated direct wide-forbidden-band inorganic semiconductor material with a lead-zinc ore structure, the appearance of the whisker is white loose powder, the whisker is in a three-dimensional four-needle three-dimensional structure, the whisker is provided with a core, four needle crystals extend from the radial direction of the core, each needle is single crystal microfiber, and the whisker only has a space three-dimensional structure in all whiskers so far, because of the unique three-dimensional four-needle three-dimensional structure, the whisker can be easily uniformly distributed in a matrix material, thereby isotropically improving the physical property of the material and simultaneously endowing the material with a plurality of unique functional characteristics. The zinc oxide has excellent properties which are incomparable with those of common zinc oxide, such as wear resistance, reinforcement, vibration reduction, skid resistance, noise reduction, wave absorption, ageing resistance, static resistance, antibiosis and the like, and can be widely used in the national economic fields of electronics, chemical industry, light industry, traffic and the like.
At present, the preparation method of the tetrapod-like zinc oxide whisker mainly comprises the following steps:
the first method is a zinc powder pre-oxidation method. The method is adopted by Japanese pine company which develops tetrapod-like zinc oxide whisker successfully, the technological process is that zinc powder is pre-oxidized for 72 hours to cover a layer of oxide film on the surface, and then the zinc powder with the oxide film is heated for about a certain time at about 1000 ℃ to prepare T-ZnOw. The method mainly inhibits the molten zinc metal from flowing out of the interior of the particles rapidly by forming a surface oxide film, and simultaneously inhibits the too fast migration of oxygen into zinc particles, thereby ensuring the conditions required by the growth of single crystals. The method has the defects of long production period, low income, high cost, complex process and more finished product platelets.
The second method is an equilibrium gas flow method invented by southwest province, which adopts zinc particle raw materials to reduce the oxygen flow in the furnace according to the principle of air thermal expansion, adopts double reaction boxes to alternately perform, and completes the reaction process at 600-1100 ℃. The method has the defects of small scale, intermittent production, low income, low needle formation rate, large number of platelets, high production strength and strong randomness of atmosphere control.
The third method is inert gas protection method, mainly heating zinc powder to above boiling point under the protection of inert gas, then using inert gas as carrier gas, introducing zinc steam into oxygen-containing gas or blowing oxygen-containing gas into zinc steam, and making zinc steam and oxygen produce gas phase contact reaction to produce zinc oxide whisker. The disadvantage of this process is the large consumption of inert gas, the difficulty in precise control of the reaction and the extremely high demands on personnel and equipment.
The fourth method is to use metallic zinc as raw material, add carbon powder as oxygen consumption regulator, utilize the reducibility of carbon, consume a part of oxygen in the air around zinc, make zinc oxidize under the relative anoxic condition to produce zinc oxide whisker. The disadvantage of this method is that the atmosphere is difficult to control and the yield is low.
The preparation process of T-ZnOw of Chinese patent ZL02113881.1 includes heating industrial zinc ingot as material in high temperature melting unit at 700-1000 deg.c to melt, volatilizing, introducing zinc vapor into whisker reactor with nitrogen, reaction with mixed gas of nitrogen and air, controlling the reaction speed to crystallize and grow zinc oxide to form four needle zinc oxide whisker, cooling with nitrogen and separating product.
The Chinese patent ZL98111828.3 utilizes the principle of thermal expansion of gas to reduce the oxygen amount in the furnace, takes zinc particles as raw materials, uses double reaction boxes to alternately perform, completes the continuous production process at 600-1100 ℃, and has the product yield of more than 90%, wherein more than 95% is tetrapod-like zinc oxide whisker.
The Chinese patent ZL99112867.2 uses white carbon black as a catalyst, and the pretreated metal zinc powder and the white carbon black are mixed in a hot air environment at 900-1000 ℃ to generate the tetrapod-like zinc oxide whisker.
The preparation methods of the T-ZnOw are difficult to realize large-scale production, and the purity and quality of the product cannot be effectively ensured. In addition, the four needle-shaped zinc oxide whiskers produced by Japanese pine company and southwest China are all characterized by low whisker conversion rate, low direct yield and the like, so that the production cost is increased.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing tetrapod-like zinc oxide whiskers by using a modified montmorillonite catalyst, which comprises the following steps:
s1, putting a modified montmorillonite catalyst into a catalyst bin from a catalyst bin opening, and preheating at 500-1100 ℃, wherein the mass fraction of montmorillonite is 90.5%;
s2, putting zinc particles into a raw material bin, heating by a heater to enable the zinc particles to be equal to the temperature of a catalyst bin, wherein the purity of the zinc particles is 99%;
s3, the modified montmorillonite catalyst enters a raw material bin through a connecting hole on a separation plate in a steam mode, and zinc steam is combined on the upper layer of the raw material bin;
s4, controlling the rotating speed of a stirring blade to be 5-15 revolutions per minute by utilizing an intelligent variable frequency system, fully mixing catalyst vapor and zinc vapor, accelerating zinc oxide crystal growth by positive charge ion exchange, reacting for 10-25 minutes, and introducing functional gas into the reactor through a pressurizing pipeline when the reaction is carried out for 7 minutes to form tetrapod-like zinc oxide whiskers;
s5, stacking the tetrapod-like zinc oxide whiskers formed by the reaction at a material isolation plate, and extracting and collecting the tetrapod-like zinc oxide whiskers to a finished product recovery container by utilizing a finished product recovery channel, wherein the catalyst after the reaction falls into the bottom of the catalyst bin in a form of massive crystals through a connecting hole, and extracting and collecting the tetrapod-like zinc oxide whiskers to the catalyst recovery container through the catalyst recovery channel.
Preferably, the preparation process of the modified montmorillonite comprises the following steps:
s11, mixing bentonite raw ore with water according to a proportion of 1:10, and then adding phosphoric acid into the suspension, and then placing the suspension in a stirrer for stirring uniformly to obtain bentonite ore pulp, wherein the mass ratio of the addition amount of the phosphoric acid to raw water is 1:10.
S12, transferring bentonite ore pulp into a stirring device for stirring, and simultaneously treating the ore pulp by using an ultrasonic dispersing instrument to fully disperse the bentonite in water, wherein the temperature of the ultrasonic dispersing treatment ore pulp is 30 ℃, the treatment time is 70 minutes, and the bentonite dispersion liquid is obtained after the ultrasonic dispersing is finished.
S13, naturally standing the bentonite dispersion liquid, separating out and filtering slurry on the upper layer of the dispersion liquid after impurities in the dispersion liquid are settled to obtain a bentonite filter cake, drying the filter cake by using a spray dryer, and crushing a filter material by using a crusher to obtain a bentonite purified material.
S14, uniformly mixing and stirring 100 parts by weight of bentonite purification, 20 parts by weight of sulfuric acid and 400 parts by weight of water to obtain a bentonite mixture, carrying out radiation reaction on the mixture by using a microwave radiator, wherein the power of the microwave radiator is 320W, the radiation reaction time is 4 minutes,washing the mixture with water until pH of the mixture is 6.5 after the radiation reaction, filtering, drying, pulverizing the mixture to powder with particle diameter of 300 meshes to obtain small pore diameter of 2-12nm with specific surface area of 140m 2 And/g, modified montmorillonite catalyst with skeletal channels dredged and modified.
Preferably, the modified montmorillonite catalyst and zinc particles are mixed according to a ratio of 3:10 are respectively placed in a quartz boat and added into a reactor.
Preferably, the functional gas is a mixed gas of oxygen and nitrogen,
preferably, the volume ratio of the oxygen to the nitrogen is 4:6.
The invention also provides equipment for preparing the tetrapod-like zinc oxide whisker by using the modified montmorillonite catalyst, which is a whisker reactor designed mainly according to the crystallization and growth mechanism of the tetrapod-like zinc oxide whisker, and can effectively improve the stability, the continuity and the whisker conversion rate of the production process and greatly reduce the production cost. The four-needle zinc oxide whisker equipment comprises a reaction furnace, an air pressure adjusting device, a recovery device, a stirring device and a control system, wherein the air pressure adjusting device, the recovery device and the stirring device are respectively connected with the reaction furnace, and the control system is connected with the air pressure adjusting device; the reactor comprises a partition plate horizontally arranged in the middle of the reactor, the partition plate divides the reactor into a raw material bin and a catalyst bin from top to bottom, a plurality of through connecting holes are formed in the partition plate, and independent heaters are arranged in the catalyst bin and the raw material bin and are electrically connected with a control system.
Preferably, the air pressure adjusting device comprises a pressurizing pipeline, a depressurizing pipeline and a hot pressure meter connected with the pressurizing pipeline and the depressurizing pipeline respectively; wherein, the pressure increasing pipeline and the pressure reducing pipeline are respectively connected with the inside of the reactor.
Preferably, the stirring device comprises a stirring rod and stirring blades connected with the stirring rod and arranged in the raw material bin.
Preferably, the recovery device comprises a finished product recovery channel and a catalyst recovery channel which are arranged on the outer wall of the reaction furnace and communicated with the reactor.
Preferably, one end of the finished product recovery channel is connected with the raw material bin, and the other end of the finished product recovery channel is connected with the finished product recovery container; one end of the catalyst recovery channel is connected with the catalyst bin, and the other end of the catalyst recovery channel is connected with the catalyst recovery container.
By adopting the technical scheme, the invention has the following technical effects:
1. the pore diameter and skeleton channel inside the montmorillonite are dredged through microwave acidification modification, so that the modified montmorillonite has a larger specific surface area and a unique internal pore channel structure, the intermolecular acceleration motion and the full reaction of positive charge ions of an inorganic catalyst are promoted, the catalysis effect is achieved, energy is saved, consumption is reduced, the four-needle zinc oxide is prepared as a catalyst, zinc oxide crystal nuclei are formed to form non-uniform nucleation, the crystal nuclei and needle bodies are formed at uniform speed on four alternate triangular planes of an regular octahedral body of the crystal nuclei, the morphology of the obtained zinc oxide crystal whisker is uniform and complete, the needle formation rate is high, the crystal whisker growth is good, the crystal whisker is uniform and regular four-needle crystal whisker, and the crystal whisker is free of platelet, three-needle, five-needle and other non-four-needle crystal whiskers, and the crystal whisker size is uniform.
2. By arranging a control system in communication connection with the heater and the air pressure adjusting device, the reaction conditions in the reactor are automatically adjusted to the reaction conditions most suitable for zinc oxide crystallization according to the set parameters and the data detected by the hot pressure meter, the furnace pressure and the bin pressure are intelligently controlled, the automatic production of the tetrapod-shaped zinc oxide whiskers is realized, and the labor burden of operators is reduced.
3. The whisker has high conversion rate, more than 99.9% of the whisker is tetrapod-like zinc oxide whisker in the product obtained after the reaction is finished, meanwhile, the direct yield of the whisker product is 99%, the zinc recovery rate is more than 99%, the modified montmorillonite is used as a catalyst, and zinc particles are used as raw materials, so that the production cost is low.
4. The intelligent separation and connection of the raw materials and the catalyst are realized by arranging the isolation plate with the connecting holes and the independent recovery device, so that the gas generated by preheating the inorganic catalyst and zinc vapor can be subjected to positive charge ion exchange, the formation of tetrapod-like zinc oxide whiskers is accelerated, and the tetrapod-like zinc oxide whiskers can be effectively separated from the whiskers after catalysis.
Drawings
FIG. 1 is a schematic diagram of the connection structure of the tetrapod-like zinc oxide whisker apparatus of the present invention;
FIG. 2 is a schematic structural diagram of a reaction furnace in the tetrapod-like zinc oxide whisker equipment of the present invention;
FIG. 3 is a flow chart of a process for preparing tetrapod-like zinc oxide whiskers from the modified montmorillonite catalyst of the invention;
FIG. 4 is a scanning electron microscope image of a tetrapod-like zinc oxide whisker of the comparative example of the present invention;
FIG. 5 is a scanning electron microscope image of the tetrapod-like zinc oxide whiskers prepared in example 1 of the present invention;
FIG. 6 is a scanning electron microscope image of the tetrapod-like zinc oxide whiskers produced in example 2 of the present invention;
wherein the reference numerals have the following meanings:
1. a reaction furnace;
2. a reactor; 21. a partition plate; 211. a connection hole; 22. a catalyst bin; 23. a raw material bin;
3. an air pressure adjusting device; 31. a pressurizing pipe; 32. a pressure reducing pipe;
4. a recovery device; 41. a finished product recovery channel; 42. a catalyst recovery channel;
5. a stirring device; 51. a stirring rod; 52. stirring the leaves;
6. and a control system.
Detailed Description
In order that those skilled in the art will better understand the present invention, a detailed description of embodiments of the present invention will be provided below, together with the accompanying drawings, wherein it is evident that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the invention. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
Referring to fig. 1-2, the invention provides equipment for preparing tetrapod-like zinc oxide whisker by using a modified montmorillonite catalyst, which comprises a reaction furnace 1, an air pressure adjusting device 3, a recovery device 4, a stirring device 5 and a control system 6, wherein the air pressure adjusting device 3, the recovery device 4 and the stirring device 5 are respectively connected with the reaction furnace 1, and the control system 6 is in communication connection with the air pressure adjusting device 3.
The reactor 1 is internally provided with a reactor 2 with an inverted triangle-shaped cross section, the reactor 2 comprises a separation plate 21 horizontally arranged in the middle of the reactor 2, a plurality of through connecting holes 211 are arranged on the separation plate 21, the separation plate 21 divides the inverted triangle-shaped reactor 2 into an upper area and a lower area, wherein the area below the separation plate 21 is a catalyst bin 22 for placing catalyst modified montmorillonite required for preparing tetrapod-shaped zinc oxide whiskers, and the cross section of the catalyst modified montmorillonite is an inverted triangle; the upper area is a raw material bin 23 for placing raw materials for producing the tetrapod-like zinc oxide whiskers, the cross section of the raw materials is in an inverted trapezoid shape, and zinc particles and the modified montmorillonite catalyst are separated before the reaction by arranging a separation plate 21, so that operators can conveniently add the zinc particles and the modified montmorillonite catalyst into the reactor 2 respectively. Wherein, the catalyst bin 22 and the raw material bin 23 are respectively provided with a heater (not shown in the figure), and the heaters are electrically connected with the control system 6 and used for adjusting the temperature in the catalyst bin 22 and the raw material bin 23, so as to change the state (solid, liquid and gas three states) of the zinc particles or the modified montmorillonite catalyst. The quartz boat is used for containing zinc particles and then is arranged in a raw material bin 23, the quartz boat is used for containing modified montmorillonite catalysts and then is arranged in a catalyst bin 22, wherein the quartz boat containing zinc particles is positioned at 2/3 of the height of the raw material bin 23, the modified montmorillonite catalysts heated to a gaseous state are mixed with zinc vapor and functional gas by rising from the catalyst bin 22 to the raw material bin 23 through connecting holes 211, so as to catalyze the reaction for preparing the tetrapod-shaped zinc oxide whiskers, the tetrapod-shaped zinc oxide whiskers generated in the reaction are accumulated on a separation plate 21, and the catalysts after the reaction drop from the raw material bin 23 to the catalyst bin 22 in a block crystallization mode through the connecting holes 211. The pressure of the reaction bin and the flow exchange property of the catalyst are controlled in the reactor 2, so that the charge exchange speed is ensured, the tetrapod-like zinc oxide whisker is taken as a core, inorganic catalyst vapor and zinc vapor form a spiral movement state to carry out positive charge ion exchange, the inorganic catalyst vapor grows up in the spiral movement process, larger crystals are formed, the tetrapod-like zinc oxide whisker is formed, and the quality of the whisker is improved.
Further, the air pressure adjusting device 3 comprises a pressurizing pipeline 31 and a depressurizing pipeline 32 which are arranged on the outer wall of the reaction furnace 1 and communicated with the reactor 2, and a hot pressure gauge which is respectively connected with the pressurizing pipeline 31 and the depressurizing pipeline 32, wherein the pressurizing pipeline 31 and the depressurizing pipeline 32 are both U-shaped, the pressurizing pipeline 31 is used for introducing functional gas into the reactor 2, and then the reaction conditions for preparing the tetrapod-shaped zinc oxide whisker in the reactor 2 are adjusted, so that zinc oxide is crystallized, and the tetrapod-shaped zinc oxide whisker is obtained.
Specifically, one end of the pressurizing pipe 31 is connected to the inside of the reactor 2, the other end is connected to a heat pressure gauge (not shown), and one end of the depressurizing pipe 32 is connected to the inside of the reactor 2, and the other end is connected to the heat pressure gauge (not shown). Wherein the hot pressure gauge is used for detecting the reaction conditions inside the reactor 2, preferably, the reaction conditions comprise pressure and temperature, according to the data fed back by the hot pressure gauge, an operator can adjust the reaction conditions in the reactor 2 to the reaction conditions suitable for zinc oxide crystallization by using the air pressure adjusting device 3 and the heater in the reaction process, wherein the pressurizing pipeline 31 is used for introducing functional gas into the reactor 2, the depressurizing pipeline 32 is used for recovering the functional gas in the reactor 2, and the reaction conditions in the reactor 2 are adjusted by introducing or recovering the functional gas into the reactor 2 and adjusting the heater in the reactor 2, so that the zinc oxide crystals are obtained to obtain the tetrapod-like zinc oxide whiskers.
Further, in this embodiment, the control system 6 is further connected to the air pressure adjusting device 3 and the heater in a communication manner, and according to the data fed back by the thermal pressure gauge and the preset parameters, the control system 6 can automatically send out the instructions for opening and closing the pressurizing pipe 31, the depressurizing pipe 32 and the heater independently or simultaneously, so as to adjust the reaction conditions in the reactor 2 to the reaction conditions most suitable for zinc oxide crystallization. Preferably, in this embodiment, the control system is a PLC program, and by setting the PLC program, the automatic adjustment of the reaction condition of 2 in the reactor is facilitated, the furnace pressure and the bin pressure are intelligently controlled, and the automatic production of the tetrapod-like zinc oxide whisker is realized, so as to reduce the labor burden of operators.
Stirring device 5 include puddler 51 and with stirring leaf 52 that stirring rod 51 links to each other, wherein, stirring rod 51's one end pass the furnace body of reacting furnace 1 stretch into raw materials material storage bin 23 in with stirring leaf 52 link to each other, the other end is connected with intelligent frequency conversion system and is used for controlling stirring speed, stirring leaf 52 circular telegram back is rotatory, and then the air flow in the raw materials storage bin 23 is accelerated, under stirring leaf 52's stirring effect, zinc vapor, gaseous catalyst and functional gas intermolecular accelerated motion, make zinc vapor, gaseous catalyst and functional gas intensive mixing, and then promote positive charge ion reaction, promote catalytic reaction's going on, improve the production efficiency of preparing tetrapod zinc oxide whisker.
The recovery device 4 comprises a finished product recovery channel 41 and a catalyst recovery channel 42, wherein one end of the finished product recovery channel 41 is connected with the raw material bin 23, the other end of the finished product recovery channel is connected with a finished product recovery container (not shown in the figure), one end of the catalyst recovery channel 42 is connected with the catalyst bin 22, the other end of the catalyst recovery channel is connected with the catalyst recovery container (not shown in the figure), and an operator can recover the tetrapod-shaped zinc oxide whiskers or the catalyst by using a pumping pump (not shown in the figure). Through setting up division board 21, can let inorganic catalyst preheat the gas that produces and carry out positive charge ion reaction with zinc vapor, the acceleration forms four needle-shaped zinc oxide whisker, can also separate four needle-shaped zinc oxide whisker finished product and catalyst simultaneously after the reaction is over, when making things convenient for operating personnel to add raw materials and catalyst, also conveniently retrieve four needle-shaped zinc oxide whisker's finished product and catalyst alone.
The four-needle zinc oxide whisker equipment is utilized to prepare the four-needle zinc oxide whisker, the catalyst and zinc are mixed with the functional gas in a gaseous state, so that the catalyst is fully contacted with reactants, the whisker conversion rate is high, more than 99.9% of the product obtained after the reaction is finished is the four-needle zinc oxide whisker, the process flow is intelligent, and meanwhile, the direct yield of whisker products is 99%, the zinc recovery rate is more than 99%, and the production cost is low. The production process provided by the invention is easy to realize continuous and automatic intelligent production of the whole process, and ensures the stability of the product quality.
The invention also provides a method for preparing the tetrapod-like zinc oxide whisker by using the modified montmorillonite catalyst, which comprises the following steps:
example 1:
the invention adopts modified montmorillonite as a catalyst to prepare tetrapod-like zinc oxide whisker, which comprises the following steps:
s1, putting a modified montmorillonite catalyst into a catalyst bin from a catalyst bin opening, and preheating at 500-1100 ℃, wherein the mass fraction of montmorillonite is 90.5%;
s2, zinc particles are put into a raw material bin and heated by a heater to be equal to the temperature of a catalyst bin, and the purity of the zinc particles is 99%;
s3, enabling the catalyst to enter a raw material bin through a connecting hole on the isolation plate in a steam mode, and combining zinc steam on the upper layer of the raw material bin;
s4, controlling the rotating speed of a stirring blade to be 5-15 revolutions per minute by utilizing an intelligent variable frequency system, fully mixing catalyst vapor and zinc vapor, accelerating zinc oxide crystal growth by positive charge ion exchange, reacting for 10-25 minutes, and introducing functional gas into the reactor through a pressurizing pipeline when the reaction is carried out for 7 minutes to form tetrapod-like zinc oxide whiskers;
s5, stacking the tetrapod-like zinc oxide whiskers formed by the reaction at a material isolation plate, and extracting and collecting the tetrapod-like zinc oxide whiskers to a finished product recovery container by utilizing a finished product recovery channel, wherein the catalyst after the reaction falls into the bottom of the catalyst bin in a form of massive crystals through a connecting hole, and extracting and collecting the tetrapod-like zinc oxide whiskers to the catalyst recovery container through the catalyst recovery channel.
Wherein, the preparation process of the modified montmorillonite comprises the following steps:
s11, mixing bentonite raw ore with water according to a proportion of 1:10, and then adding phosphoric acid into the suspension, and then placing the suspension in a stirrer for stirring uniformly to obtain bentonite ore pulp, wherein the mass ratio of the addition amount of the phosphoric acid to raw water is 1:10.
S12, transferring bentonite ore pulp into a stirring device for stirring, and simultaneously treating the ore pulp by using an ultrasonic dispersing instrument to fully disperse the bentonite in water, wherein the temperature of the ultrasonic dispersing treatment ore pulp is 30 ℃, the treatment time is 70 minutes, and the bentonite dispersion liquid is obtained after the ultrasonic dispersing is finished.
S13, naturally standing the bentonite dispersion liquid, separating out and filtering slurry on the upper layer of the dispersion liquid after impurities in the dispersion liquid are settled to obtain a bentonite filter cake, drying the filter cake by using a spray dryer, and crushing a filter material by using a crusher to obtain a bentonite purified material.
S14, mixing 100 parts by weight of bentonite purification, 20 parts by weight of sulfuric acid and 400 parts by weight of water uniformly to obtain a bentonite mixture, carrying out radiation reaction on the mixture by using a microwave radiator, wherein the power of the microwave radiator is 320W, the radiation reaction time is 4 minutes, washing the mixture by using water until the pH value in the mixture is 6.5 after the radiation reaction is finished, filtering and drying the mixture, and crushing the mixture to powder with the particle size of 300 meshes (namely 48 mu m), thereby obtaining a small pore diameter of 2-12nm and a specific surface area of 140m 2 And/g, modified montmorillonite catalyst with skeletal channels dredged and modified.
Wherein, the modified montmorillonite catalyst and zinc particles are mixed according to the proportion of 3:10 are respectively placed in a quartz boat and added into a reactor.
The functional gas is a mixed gas of oxygen and nitrogen, wherein the volume ratio of the oxygen to the nitrogen is 4:6.
Example 2:
example 2 differs from example 1 only in that the mass fraction of montmorillonite in the modified montmorillonite catalyst is 78%, and the rest of the procedure is the same as in example 1.
Comparative example:
the finished product produced by the japanese pine company was used as a control.
The principle of the present invention using montmorillonite as a catalyst for preparing tetrapod-like zinc oxide whiskers is further described below.
Bentonite is a nonmetallic mineral product with montmorillonite as a main mineral component, wherein montmorillonite belongs to one of smectite group minerals, and is generally in a block shape or a soil shape. Molecular formula (Na, ca) 0.33 (Al, mg) 2 [Si 4 O 10 ](OH) 2 ·nH 2 O, the middle is an aluminum oxide octahedron, the upper and lower are clay minerals with a three-layer lamellar structure formed by silicon oxygen tetrahedrons, montmorillonite crystals belong to water-containing lamellar structure silicate minerals of monoclinic system, the bentonite is defined as bentonite with the montmorillonite content lower than 80% in the industry in China, and the montmorillonite with the montmorillonite content higher than 80%.
According to the invention, after the montmorillonite is purified from bentonite, the montmorillonite is subjected to microwave acidification modification treatment, the pore diameter and skeleton channel inside the montmorillonite are dredged by utilizing the microwave acidification modification, the modified montmorillonite catalyst has a larger specific surface area and a unique internal pore structure, and the structural layers of the crystal of the montmorillonite catalyst contain water and positive charge cations, so that the montmorillonite catalyst has higher ion exchange capacity.
Further, the high-purity montmorillonite has a layered structure and non-uniform charge distribution, so that in the process of preparing the tetrapod-like zinc oxide whisker, the montmorillonite has positive charges and zinc generate charge reaction, and the montmorillonite and the zinc oxide have positive charges, and commonly known, the charges with the same polarity are mutually repelled, so that zinc oxide molecules formed in the atmosphere around the zinc oxide crystal nucleus have greatly reduced probability of collision under the action of repulsive force, so that the growth speed of the ZnO crystal nucleus and a needle body tends to be balanced, the growth of the whisker is promoted and tends to be complete while the reaction speed is accelerated,
specifically, the dehydration temperature of the modified montmorillonite catalyst is higher, the heat absorption valley appears between 600 and 700 ℃, the montmorillonite catalyst takes off structural water, the second heat absorption valley is between 800 and 935 ℃, and the crystal lattice of the modified montmorillonite catalyst is completely destroyed. Then the zinc oxide whisker with white loose appearance is produced by catalysis at 900-1100 deg. Because the generated zinc oxide whisker has a tetrapod-like structure, the aggregate is difficult to be closely piled and is loose, a great amount of heat released by the oxidation reaction for preparing the tetrapod-like zinc oxide whisker is needed to expand the gas in the reactor so as to drive the generated tetrapod-like zinc oxide whisker to leave the raw material zinc and the reaction zone to the isolation plate, and in the reaction furnace, the air outside the reactor enters the reaction zone by means of concentration gradient caused by the reaction, so that the transportation of oxygen of a gas material is completed.
In the invention, zinc oxide crystal nucleus forms non-uniformity nucleation under the action of proper temperature, environment and proper amount of modified montmorillonite catalyst, and crystal nucleus and needle body form uniformly on four alternate triangular planes of regular octahedron of crystal nucleus, so that the morphology of the obtained zinc oxide whisker is uniform and complete.
The morphology structures of the corresponding tetrapod-like zinc oxide whiskers obtained by SEM observation of the finished products obtained in comparative examples and examples 1-2 are shown in the accompanying drawings 4-6 of the specification, and the SEM photograph of the tetrapod-like zinc oxide whiskers obtained in comparative examples is shown in fig. 4, wherein the whisker growth is poor, the whisker morphology obtained is irregular and different in size, the columnar whisker morphology is more, and the needle-like whisker morphology is less. Fig. 5 is an SEM photograph of the tetrapod-like zinc oxide whisker obtained in example 1, which has a high needle formation rate and good whisker growth, is a uniform tetrapod-like whisker, has no platelet, three needles, five needles, and other non-tetrapod whiskers, and has a uniform whisker size. The average value is calculated through twenty visual fields, the regularity of the four needle-shaped whisker is 99.9%, the length of each needle is 30-45 mu m, the diameter of the root is 2-5 mu m, and the included angle of every two needles is 109 degrees. FIG. 6 is a SEM photograph of four needle-shaped zinc oxide whiskers obtained in example 2, which shows that the whiskers are better in growth and higher in needle-forming rate than comparative example 1, but the phenomena of platelet and four needle growth are not formed.
In conclusion, the modified montmorillonite is used as the catalyst for preparing the tetrapod-like zinc oxide whiskers, and in the modification process, the pore diameter and specific surface area of the montmorillonite catalyst are controlled to be the same, the montmorillonite content is different, the catalysis effect of the catalyst with higher montmorillonite content is more excellent, and the obtained tetrapod-like zinc oxide whisker finished product has high needle formation rate, perfect product phase and no platelet, and almost achieves an ideal form.
Finally, it should be noted that: the embodiment of the invention is disclosed only as a preferred embodiment of the invention, and is only used for illustrating the technical scheme of the invention, but not limiting the technical scheme; although the invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand that; the technical scheme recorded in the various embodiments can be modified or part of technical features in the technical scheme can be replaced equivalently; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (4)
1. The method for preparing the tetrapod-like zinc oxide whiskers by using the modified montmorillonite catalyst is characterized in that equipment for preparing the tetrapod-like zinc oxide whiskers by using the modified montmorillonite catalyst comprises a reaction furnace (1), and air pressure regulating equipment (3), a recovery device (4) and a stirring device (5) which are respectively connected with the reaction furnace (1); a reactor (2) is arranged in the reaction furnace (1); the reactor (2) comprises a separation plate (21) horizontally arranged in the middle of the reactor (2), the separation plate (21) divides the reactor (2) into a raw material bin (23) and a catalyst bin (22) from top to bottom, a plurality of through connecting holes (211) are formed in the separation plate (21), and independent heaters are arranged in the catalyst bin (22) and the raw material bin (23);
the air pressure regulating device (3) comprises a pressurizing pipeline (31); wherein the pressurizing pipe (31) is connected with the inside of the reactor (2);
the stirring device (5) comprises stirring blades (52) arranged in the raw material bin (23);
the recovery device (4) comprises a finished product recovery channel (41) and a catalyst recovery channel (42) which are arranged on the outer wall of the reaction furnace (1) and communicated with the reactor (2); one end of the finished product recovery channel (41) is connected with the raw material bin (23), and the other end of the finished product recovery channel is connected with a finished product recovery container; one end of the catalyst recovery channel (42) is connected with the catalyst bin (22), and the other end is connected with the catalyst recovery container;
the method comprises the following steps:
s1, putting the modified montmorillonite catalyst into a catalyst bin from a catalyst bin opening, wherein the mass fraction of montmorillonite is 90.5%, preheating is carried out at 500-1100 ℃, the modified montmorillonite catalyst takes off structural water at 600-700 ℃, the crystal lattice of the modified montmorillonite catalyst is completely destroyed at 800-935 ℃, and zinc is catalyzed to generate white loose zinc oxide whiskers at 900-1100 ℃;
s2, zinc particles are put into a raw material bin and heated by a heater to be equal to the temperature of a catalyst bin, and the purity of the zinc particles is 99%;
s3, the modified montmorillonite catalyst enters a raw material bin through a connecting hole on a separation plate in a steam mode, and zinc steam is combined on the upper layer of the raw material bin;
s4, controlling the rotating speed of the stirring blade to be 5-15 revolutions per minute by utilizing an intelligent variable frequency system, fully mixing catalyst vapor and zinc vapor, accelerating zinc oxide crystal growth by positive charge ion exchange, reacting for 10-25 minutes, and introducing functional gas into the reactor through a pressurizing pipeline when the reaction is carried out for 7 minutes to form tetrapod-like zinc oxide whiskers;
s5, stacking the tetrapod-like zinc oxide whiskers formed by the reaction at a material isolation plate, extracting and collecting the tetrapod-like zinc oxide whiskers to a finished product recovery container by utilizing a finished product recovery channel, dropping the reacted catalyst into the bottom of a catalyst bin in a form of massive crystals, and extracting and collecting the catalyst to the catalyst recovery container by utilizing the catalyst recovery channel;
wherein, the preparation process of the modified montmorillonite comprises the following steps:
s11, mixing bentonite raw ore with water according to a proportion of 1:10, preparing a suspension, adding phosphoric acid into the suspension, and then placing the suspension in a stirrer for stirring uniformly to obtain bentonite ore pulp, wherein the mass ratio of the addition amount of the phosphoric acid to raw material water is 1:10;
s12, transferring bentonite ore pulp into a stirring device for stirring, and simultaneously, treating the ore pulp by using an ultrasonic dispersing instrument to fully disperse the bentonite in water, wherein the temperature of the ultrasonic dispersing treatment ore pulp is 30 ℃, the treatment time is 70 minutes, and bentonite dispersion liquid is obtained after ultrasonic dispersing is finished;
s13, naturally standing the bentonite dispersion liquid, separating out and filtering slurry on the upper layer of the dispersion liquid after impurities in the dispersion liquid are settled to obtain a bentonite filter cake, drying the filter cake by a spray dryer, and crushing the filter material by a crusher to obtain a bentonite purified material;
s14, mixing 100 parts by weight of bentonite purification, 20 parts by weight of sulfuric acid and 400 parts by weight of water uniformly to obtain a bentonite mixture, carrying out radiation reaction on the mixture by using a microwave radiator, wherein the power of the microwave radiator is 320W, the radiation reaction time is 4 minutes, washing the mixture by using water until the pH value in the mixture is 6.5 after the radiation reaction is finished, filtering and drying, and crushing the mixture to powder with the particle size of 300 meshes to obtain a small pore diameter of 2-12nm and a specific surface area of 140m 2 And/g, modified montmorillonite catalyst with skeletal channels dredged and modified.
2. The method for preparing tetrapod-like zinc oxide whiskers by using a modified montmorillonite catalyst according to claim 1, wherein the modified montmorillonite catalyst and zinc particles are prepared according to a ratio of 3:10 are respectively placed in a quartz boat and added into a reactor.
3. The method for preparing tetrapod-like zinc oxide whiskers by using the modified montmorillonite catalyst according to claim 2, wherein the functional gas is a mixed gas of oxygen and nitrogen.
4. A method for preparing tetrapod-like zinc oxide whiskers with a modified montmorillonite catalyst according to claim 3, wherein the volume ratio of oxygen to nitrogen is 4:6.
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