CN1834021A - Prepn. process of mesic hole hollow ball-shape titania powder - Google Patents
Prepn. process of mesic hole hollow ball-shape titania powder Download PDFInfo
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Abstract
This invention relates to a method to prepare mezoporous empty-centered titanium dioxide powders, which comprises following steps: titanium chloride is made into hydrosol with pure water, diluted and introduced into a spray dryer for spray drying. The subsequent product is empty-centered ball-shaped powder made up of nanosized titanium dioxide particles and the preceding titanium chloride is titanium tetrachloride or titanium trichloride. The titanium dioxide particles prepared in this invention all have mezoporous empty-centered ball-shaped structure and the empty-centered wall is made up of nanosized titanium dioxide particles and mezopores, on the surface of which titanium atoms possess a fraction of as high as 70%. As only titanium tetrachloride is adopted as precursor and no other reagent is necessary, the product is highly pure and has excellent photocatalytic properties. This method has the advantages of high yield, low cost, easily controlled technique and convenience for magnification experiment. Besides, there are not severe requirements for facilities and this method is suitable for industrial production.
Description
(1) technical field
The present invention relates to a kind of preparation method of mesic hole hollow ball-shape titania powder.
(2) background technology
Since the preparation of nineteen ninety-five report poriferous titanium dioxide powder, because it is of many uses, the filler that both can be used as low-k and low-gravity matrix material, also can be used as slowly-releasing and put the carrier of microcapsule system and drug delivery, in catalytic field, also catalyzer can be filled into hollow in to improve catalytic performance.Therefore, its preparation has caused concern widely.At present, existing many reports in the domestic and foreign literature about the poriferous titanium dioxide powder preparation method, but these methods all are based upon on the basis of template, need be template promptly with Mierocrystalline cellulose, little micella, the poly-third ethene microballoon or little supernatant liquid, and in subsequent processes, adopt methods such as calcining or solvent corrosion that above-mentioned template is removed, can generate vesicular structure.
Mesic hole hollow ball-shape titania causes domestic and international experts and scholars' attention because of having broad application prospects in fields such as effective catalyst, solar cell, aqueous electrochemical photolysis and semi-conductors.In recent years, many bibliographical informations about the mesic hole hollow ball-shape titania powder preparation method are arranged.But, in these preparation methods, all need to use organism, as propyl alcohol, ter-polymers, or inorganic materials is as auxiliary agent and pore-forming material, and in subsequent processes these auxiliary agents or pore-forming material removed and could generate meso-hole structure.In addition, also having with organism such as tensio-active agents is auxiliary agent, at first titanium dioxide is prepared into stratiform, by technological methods such as self-assemblies laminar titanium dioxide is built into the bibliographical information of mesic hole hollow ball-shape structure then.
The preparation method of above-mentioned mesic hole hollow ball-shape titania powder need be auxiliary agent and pore-forming material with tensio-active agent, polymkeric substance and inorganic materials etc. all, by in subsequent processes these auxiliary agents and pore-forming material removal being produced porousness hollow ball-shape structure.This can cause impurity residual, and impurity such as residual or positively charged ion remains in the mesic hole hollow ball-shape titania powder as carbon.These remaining impurities can change the catalytic performance and the photocatalysis performance of mesic hole hollow ball-shape titania powder, thereby influence applying of titanium dioxide powder industry and environment protection aspect.For titanium dioxide is made the best of one's way to practical application, the titanium dioxide powder that the preparation cleaning surfaces has the meso-hole structure hollow ball-shape is one of effective way.Because existing research data shows, when titanium dioxide carries out photocatalysis, the surface adsorbed oxygen primary condition that is absolutely necessary; Under cold condition, work as O
2When being adsorbed onto titanium dioxide surface, often be adsorbed on the titanium atom top on titanium dioxide granule surface; Titanium dioxide surface titanium atom adsorb oxygen is many more to help its photocatalysis more.If the titanium dioxide granule surface has impurity residual, must influence oxygen at titanium dioxide surface, the especially absorption on titanium atom, and then influence the performance of titanium dioxide optical catalyst.Therefore, in order to improve photocatalysis performance, the surface of titanium dioxide should have exposed titanium atom as much as possible.Studies show that the preparation method of titanium dioxide is to its surface property, especially its surperficial chemical constitution has significant effects; Research also shows, with the titanium chloride is raw material, promptly adopt the titanium dioxide of chloride process preparation, the titanium dioxide that the titanium atom ratio shared on its surface prepares apparently higher than other method of employing, its photocatalysis performance is apparently higher than the titanium dioxide that adopts other method preparation.Therefore, research invention is adopted chloride process to prepare the mesic hole hollow ball-shape titania photocatalyst to have actual application value.
In sum, prepare surperficial titanium atom content height, and not have other impurity, the titanium dioxide with mesic hole hollow ball-shape structure be to improve its photocatalysis performance, expand the titanium dioxide key of Application Areas in daily life.This is a subject matter to be solved by this invention, also is foothold of the present invention and starting point.
(3) summary of the invention
The purpose of this invention is to provide a kind of surperficial titanium atom content height, impurity is few, the mesic hole hollow ball-shape titania powder preparation method that photocatalytic activity is good.
For realizing the object of the invention, the technical solution adopted in the present invention is as follows:
A kind of preparation method of mesic hole hollow ball-shape titania powder, comprise the steps: the muriate of titanium is mixed with the water-sol with pure water, carry out spraying drying in the spraying drying instrument with importing to after the water-sol dilution, products therefrom i.e. hollow spherical powder for being made of titanium dioxide granule, and the muriate of described titanium is titanium tetrachloride or titanous chloride.Titanium dioxide granule on the prepared hollow spherical powder of the present invention is nano level, and described pure water is deionized water or distilled water.
Comparatively concrete, the preparation method of described mesic hole hollow ball-shape titania powder makes by following processing step:
(A) press the muriate of titanium and pure water with 1: 1～4 volume ratio, the muriate with titanium under 0～60 ℃ is added drop-wise in the pure water, fully stirs and makes colloidal sol;
(B) colloidal sol that step (A) made was placed 0 hour to 15 days, and press colloidal sol and pure water again 1: 0.5～4 volume ratio dilution is added drop-wise to pure water in the colloidal sol under 0～60 ℃, and colourless transparent solution is made in abundant stirring; The colloidal sol that makes can directly be diluted to import to behind the colourless transparent solution and carry out spraying drying in the spraying drying instrument, but preferably the colloidal sol that makes can be placed for some time, as place 0.5～15 day aging after, redilution imports to and carries out spraying drying in the spraying drying instrument.
(C) keep stirring the solution that simultaneously step (B) is made and import in the spraying drying instrument, spraying drying promptly gets product, i.e. hollow spherical powder for being made of titanium dioxide nanoparticle.
Further, the preparation method of described mesic hole hollow ball-shape titania powder calcines described product again.
Further again, the preparation method of described mesic hole hollow ball-shape titania powder, the muriate of described titanium is a titanium tetrachloride, described preparation method is that (A) presses titanium tetrachloride and pure water with 1: 1～3 volume ratio, under 0～10 ℃, titanium tetrachloride is added drop-wise in the pure water, fully stirs and make colloidal sol;
(B) colloidal sol that step (A) made is placed 2 hours～36h, and press colloidal sol and pure water again 1: 1～3 volume ratio dilution is added drop-wise to pure water in the colloidal sol under 0～10 ℃, and colourless transparent solution is made in abundant stirring;
(C) keep stirring the solution that simultaneously step (B) is made and import in the spraying drying instrument, spraying drying promptly gets product, i.e. hollow spherical powder for being made of titanium dioxide nanoparticle.
(D) described product is calcined.
More specifically, the volume ratio of titanium tetrachloride described in the step (A) and pure water is 1: 2, at 0～10 ℃ of thorough mixing, obtains the colloidal sol of oyster.Behind described colloidal sol placement 2～36h, press the dilution of 1: 2 volume ratio of colloidal sol and pure water, under 0～10 ℃, pure water is added drop-wise in the colloidal sol, thorough mixing is made colourless transparent solution, and gained solution continues to stir 0.5～2h.
Further again, the preparation method of described mesic hole hollow ball-shape titania powder is that described spray-dired processing condition are: solution inlet flow velocity is 10～20ml/min, and the gas inlet flow velocity is 25～45m
3/ h, the temperature in of hot air nozzle is 150～180 ℃, tail gas exit temperature is 90～120 ℃.Concrete, described spray-dired processing condition are: the inlet flow velocity of solution is 15ml/min, the gas inlet flow velocity is 35m
3/ h, the temperature in of hot air nozzle is 165 ℃, tail gas exit temperature is 105 ℃.When spray-dired temperature during greater than 95 ℃, hydrolysis reaction has also taken place in described solution when being dried.Here said spray-dired processing condition are directiveness, and for the spray drying device of different model, different sizes, processing condition can be different, as long as but mixing solutions successfully can be dried to powder with regard to processing condition according to the invention.
Among the preparation method of aforesaid mesic hole hollow ball-shape titania powder, the step calcining according to different can obtain the mesic hole hollow ball-shape titania powder that different crystalline phases are formed.
Described calcining is carried out as follows: be warming up to 300～500 ℃, being incubated 0.5～3 hour must be by the mesic hole hollow ball-shape titania powder of pure anatase octahedrite phase.Preferred calcination temperature is 450～500 ℃, is incubated 2 hours.
Described calcining is carried out as follows: be warming up to 550～800 ℃, be incubated 0.5～3 hour, obtain to mix the mesic hole hollow ball-shape titania powder of crystalline phase with rutile by anatase octahedrite.550～700 ℃ of preferred calcination temperature are incubated 2 hours.
Described calcining is carried out as follows: be warmed up to and be higher than 850 ℃, be incubated 1～3 hour the mesic hole hollow ball-shape titania powder of pure rutile phase.Preferred 850 ℃～1200 ℃, be incubated 2 hours.
At the pure water described in the preparation method of described mesic hole hollow ball-shape titania powder is deionized water.
More specifically, the preparation method of the hollow spherical powder of mesoporous TiO 2 particle formation carries out as follows:
A) press titanium tetrachloride and pure water with 1: 2 volume ratio, under 0～10 ℃, titanium tetrachloride is added drop-wise in the pure water, fully stir and make oyster colloidal sol;
B) with A) the oyster colloidal sol that makes placed 2～36 hours, press the dilution of 1: 2 volume ratio of colloidal sol and pure water again, under 0～10 ℃ pure water was added drop-wise in the colloidal sol, and colourless transparent solution is made in abundant stirring;
C) keep stirring simultaneously with step B) solution that makes imports in the spraying drying instrument, and spray-dired characteristic parameter is that the inlet flow velocity of titanium tetrachloride solution is 15ml/min, and the gas inlet flow velocity is 35m
3/ h, the temperature in of hot air nozzle is 165 ℃, and tail gas exit temperature is 105 ℃, and products therefrom i.e. hollow spherical powder for being made of titanium dioxide nanoparticle;
D) as required with step C) powder that makes calcines under differing temps, calcining temperature is incubated 2 hours at 450～500 ℃, acquisition be the mesic hole hollow ball-shape powder that constitutes by pure anatase octahedrite nano particle; Calcining temperature is incubated 2 hours at 550～700 ℃, obtains the mesic hole hollow ball-shape powder that is made of anatase octahedrite and two kinds of crystalline phase nano particles of rutile; Calcining temperature is incubated 2 hours at 850～1200 ℃, obtains the mesic hole hollow ball-shape powder that is made of the pure rutile nano particle.
The preparation method's of the mesic hole hollow ball-shape powder that titanium dioxide nanoparticle of the present invention constitutes technical superiority is mainly reflected in: the titanium dioxide granule for preparing all has the mesic hole hollow ball-shape structure, the hollow ball wall is to be formed by the titanium dioxide granule of nano-scale and mesoporous constructing, the ratio height that the titanium atom on titanium dioxide nanoparticle surface is shared can reach 70%; Owing to be presoma only with the titanium tetrachloride, do not need to add other any reagent, thereby the foreign matter content of product is little, the purity height, photocatalysis performance is good; The productive rate height, cost is low, and amplification test is convenient in the relatively good control of technological process; Not high to equipment requirements, be suitable for suitability for industrialized production.
(4) description of drawings
Fig. 1 is the process flow sheet of the mesic hole hollow ball-shape powder of preparation titanium dioxide nanoparticle formation of the present invention.
Fig. 2 is X-ray diffraction (XRD) figure that embodiment 1 makes the mesic hole hollow ball-shape powder that titanium dioxide nanoparticle constitutes.
Fig. 3 is scanning electronic microscope (SEM) photo that embodiment 1 makes the mesic hole hollow ball-shape powder of titanium dioxide nanoparticle formation.
(5) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto.
Embodiment 1
(1) capacity is fixed in the ice-water bath for the 500mL there-necked flask, removes ionized water 200mL and pack in the there-necked flask; On the middle port of there-necked flask, prolong is installed, is utilized the tap water condensation; The contact type thermometer is installed, with the temperature of monitoring and control reaction system on a mouth of there-necked flask; Get TiCl
4100mL packs in the exsiccant constant voltage separating funnel, the constant voltage separating funnel is installed on another side mouth of there-necked flask; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, titanium tetrachloride solution is slowly splashed in the deionized water, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 20 ℃; Adding along with titanium tetrachloride, the color of system changes gradually, be transformed into oyster by water white transparency, the viscosity of system also increases gradually, be transformed into colloidal by solution, treat that titanium tetrachloride dropwises after, continue to stir again 2 hours, this moment, mixed system was an oyster colloidal sol, with its cool to room temperature;
(2) the titanium tetrachloride water-sol is placed 12 hours aging after, get the above-mentioned colloidal sol of 100mL and pack in the there-necked flask of 500mL, there-necked flask is fixed in the water bath; On the middle port of there-necked flask, prolong is installed, is utilized the tap water condensation; The contact type thermometer is installed, with the temperature of monitoring and control reaction system on a mouth of there-necked flask; Remove ionized water 200mL and pack in the exsiccant constant voltage separating funnel, the constant voltage separating funnel is installed on another side mouth of there-necked flask; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, deionized water is slowly splashed in the sol solution, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 30 ℃; Along with the adding mixed system of deionized water is transformed into water white transparency gradually by oyster, continue again after dropwising to stir 30 minutes;
(3) solution that step (2) is made imports in the spraying drying instrument, and spray-dired characteristic parameter is that the inlet flow velocity of titanium tetrachloride solution is 15ml/min; The gas inlet flow velocity is 35m
3/ h; The temperature in of hot air nozzle is 165 ℃; Tail gas exit temperature is 105 ℃, and products therefrom is the titanium dioxide nanoparticle powder with hollow ball-shape structure;
(4) step (3) is made product and be placed in the retort furnace, be warmed up to 480 ℃, and be incubated 2 hours, obtain the mesic hole hollow ball-shape powder that is made of the anatase octahedrite nano particle after the cooling, its crystalline phase is formed as shown in Figure 2, and its granularity and pattern are as shown in Figure 3.
Embodiment 2
(1) adopts the described appliance arrangement of step (1) among the embodiment 1, get pure water (H
2O) 300mL packs in the there-necked flask; Get TiCl
4100mL packs in the exsiccant constant voltage separating funnel; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, titanium tetrachloride solution is slowly splashed in the pure water, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 5 ℃; After treating that titanium tetrachloride dropwises, continue to stir 2 hours, this moment, mixed system was an oyster colloidal sol, will place behind its cool to room temperature again;
(2) adopt the described appliance arrangement of step (2) among the embodiment 1, the titanium tetrachloride water-sol is placed 50 hours after, get the above-mentioned colloidal sol of 100mL and pack in the there-necked flask of 500mL; Get H
2O 300mL packs in the exsiccant constant voltage separating funnel; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, deionized water is slowly splashed in the sol solution, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 10 ℃; Along with the adding mixed system of pure water is transformed into water white transparency gradually by oyster, continue again after dropwising to stir 30 minutes;
(3) solution that step (2) is made imports in the spraying drying instrument, and the spraying drying parameter is with embodiment 1, and products therefrom is the titanium dioxide powder with hollow ball-shape structure;
(4) step (3) is made powder and be placed in the retort furnace, be warmed up to 700 ℃, and be incubated 2 hours, promptly get the mesic hole hollow ball-shape titania powder that constitutes by anatase octahedrite and gold redrock nano particle.
Embodiment 3
(1) adopts the described appliance arrangement of step (1) among the embodiment 1, get pure water (H
2O) 100mL packs in the there-necked flask; Get TiCl
4100mL packs in the exsiccant constant voltage separating funnel; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, titanium tetrachloride solution is slowly splashed in the pure water, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 30 ℃; After treating that titanium tetrachloride dropwises, continue to stir 2 hours, this moment, mixed system was an oyster colloidal sol, will place behind its cool to room temperature again;
(2) adopt the described appliance arrangement of step (2) among the embodiment 1, the titanium tetrachloride water-sol is placed 30 hours after, get the above-mentioned colloidal sol of 100mL and pack in the there-necked flask of 500mL; Removing ionized water 350mL packs in the exsiccant constant voltage separating funnel; Under magnetic agitation and ice-water bath refrigerative condition, open the switch of constant voltage separating funnel, deionized water is slowly splashed in the sol solution, by the temperature of controlling rate of addition and ice-water bath the temperature of whole dropping mixing process is controlled at about 35 ℃; Along with the adding mixed system of deionized water is transformed into water white transparency gradually by oyster, continue again after dropwising to stir 30 minutes;
(3) solution that step (2) is made imports in the spraying drying instrument, and the spraying drying parameter is with embodiment 1, and products therefrom is the powder with hollow ball-shape structure;
(4) step (3) is made powder and be placed in the retort furnace, be warmed up to 850 ℃, and be incubated 2 hours, promptly get the mesic hole hollow ball-shape titania powder that constitutes by the pure rutile nano particle.
Claims (10)
1. mesic hole hollow ball-shape titania powder preparation method, it is characterized in that comprising the steps: that the muriate with titanium is mixed with the water-sol with pure water, carry out spraying drying in the spraying drying instrument with importing to after the water-sol dilution, products therefrom i.e. hollow spherical powder for being made of titanium dioxide granule, and the muriate of described titanium is titanium tetrachloride or titanous chloride.
2. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 1 is characterized in that making by following processing step:
(A) press the muriate of titanium and pure water with 1: 1～4 volume ratio, the muriate with titanium under 0～60 ℃ is added drop-wise in the pure water, fully stirs and makes colloidal sol;
(B) colloidal sol that step (A) made was placed 0 hour to 15 days, and press colloidal sol and pure water again 1: 0.5～4 volume ratio dilution is added drop-wise to pure water in the colloidal sol under 0～60 ℃, and colourless transparent solution is made in abundant stirring;
(C) keep stirring the solution that simultaneously step (B) is made and import in the spraying drying instrument, spraying drying promptly gets product, i.e. hollow spherical powder for being made of titanium dioxide granule.
3. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 1 or 2 is characterized in that described product is calcined again.
4. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 3, the muriate that it is characterized in that described titanium is a titanium tetrachloride, described preparation method is:
(A) press titanium tetrachloride and pure water with 1: 1～3 volume ratio, under 0～10 ℃, titanium tetrachloride is added drop-wise in the pure water, fully stir and make colloidal sol;
(B) colloidal sol that step (A) made is placed 2 hours～36h, and press colloidal sol and pure water again 1: 1～3 volume ratio dilution is added drop-wise to pure water in the colloidal sol under 0～10 ℃, and colourless transparent solution is made in abundant stirring;
(C) keep stirring the solution that simultaneously step (B) is made and import in the spraying drying instrument, spraying drying promptly gets product, i.e. hollow spherical powder for being made of titanium dioxide granule;
(D) described product is calcined.
5. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 4 is characterized in that described spray-dired processing condition are: solution inlet flow velocity is 10～20ml/min, and the gas inlet flow velocity is 25～45m
3/ h, the temperature in of hot air nozzle is 150～180 ℃, tail gas exit temperature is 90～120 ℃.
6. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 5, it is characterized in that described spray-dired processing condition are: the inlet flow velocity of solution is 15ml/min, and the gas inlet flow velocity is 35m
3/ h, the temperature in of hot air nozzle is 165 ℃, tail gas exit temperature is 105 ℃.
7. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 3, it is characterized in that described calcining carries out as follows: be warming up to 300～500 ℃, being incubated 0.5～3 hour must be by the mesic hole hollow ball-shape titania powder of pure anatase octahedrite phase.
8. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 3, it is characterized in that described calcining carries out as follows: be warming up to 550～800 ℃, be incubated 0.5～3 hour, obtain to mix the mesic hole hollow ball-shape titania powder of crystalline phase with rutile by anatase octahedrite.
9. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 3, it is characterized in that described calcining carries out as follows: be warmed up to 850～1200 ℃, be incubated 1～3 hour the mesic hole hollow ball-shape titania powder of pure rutile phase.
10. the preparation method of mesic hole hollow ball-shape titania powder as claimed in claim 4 is characterized in that described pure water is a deionized water.
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| CN101215004B (en) * | 2008-01-18 | 2010-06-16 | 华东理工大学 | Process for preparing titanium dioxide of hollow sphere structure |
| CN101423249B (en) * | 2007-10-29 | 2011-07-27 | 中国科学院理化技术研究所 | Monodisperse pure rutile type or rutile type and anatase type composite phase titanic oxide hollow sub-micron ball and preparation method |
| CN102557126A (en) * | 2011-11-18 | 2012-07-11 | 浙江工业大学 | Sunlight-induced method for preparing fasciculate rutile titanium dioxide |
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| GB562617A (en) * | 1942-11-11 | 1944-07-10 | British Titan Products | Improvements in or relating to the hydrolytic decomposition of titanium salt solutions |
| JPH0717376B2 (en) * | 1986-06-26 | 1995-03-01 | 三菱マテリアル株式会社 | Method for producing spherical titanium dioxide powder |
| CN1210101C (en) * | 2002-03-07 | 2005-07-13 | 江苏苏净集团有限公司 | Nano titanium dioxide porous microsphere and its production method |
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| CN102557126A (en) * | 2011-11-18 | 2012-07-11 | 浙江工业大学 | Sunlight-induced method for preparing fasciculate rutile titanium dioxide |
| CN102557126B (en) * | 2011-11-18 | 2014-01-29 | 浙江工业大学 | Sunlight-induced method for preparing fasciculate rutile titanium dioxide |
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| CN104310466A (en) * | 2014-10-10 | 2015-01-28 | 常州大学 | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere |
| CN105417577A (en) * | 2015-11-06 | 2016-03-23 | 周翠华 | Method for preparing nano titanium dioxide at high temperatures |
| CN106348341A (en) * | 2016-09-18 | 2017-01-25 | 中国科学院合肥物质科学研究院 | Preparation method of titanium dioxide hollow nanospheres |
| CN107867719A (en) * | 2017-09-30 | 2018-04-03 | 常熟理工学院 | Based on hollow-core construction blueness TiO2Michaelis resonance anti-fake product and its method for anti-counterfeit |
| CN107867719B (en) * | 2017-09-30 | 2020-01-03 | 常熟理工学院 | Blue TiO based on hollow structure2Mie's resonance anti-fake product and its anti-fake method |
| CN113716576A (en) * | 2021-07-29 | 2021-11-30 | 浙江工业大学 | Method for preparing hollow spherical zeolite by using natural zeolite |
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