CN112108137B - Method for uniformly preparing attapulgite-titanium dioxide composite material - Google Patents

Method for uniformly preparing attapulgite-titanium dioxide composite material Download PDF

Info

Publication number
CN112108137B
CN112108137B CN202011118901.2A CN202011118901A CN112108137B CN 112108137 B CN112108137 B CN 112108137B CN 202011118901 A CN202011118901 A CN 202011118901A CN 112108137 B CN112108137 B CN 112108137B
Authority
CN
China
Prior art keywords
attapulgite
titanium dioxide
butyl titanate
composite material
stirring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011118901.2A
Other languages
Chinese (zh)
Other versions
CN112108137A (en
Inventor
王云霞
孟兆洁
阎逢元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN202011118901.2A priority Critical patent/CN112108137B/en
Publication of CN112108137A publication Critical patent/CN112108137A/en
Application granted granted Critical
Publication of CN112108137B publication Critical patent/CN112108137B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides a method for uniformly preparing an attapulgite-titanium dioxide composite material, belonging to the technical field of hybrid materials. The method adopts a steam hydrolysis method, magnetic stirring is assisted in the whole hydrolysis process, hydrolysis is carried out by a water bath constant temperature heating method, and the stirring speed and the water bath temperature are controlled simultaneously, so that the contact speed of the attapulgite and water vapor and the hydrolysis degree of butyl titanate are controlled, the uniformity of titanium dioxide can be ensured, the titanium dioxide in the obtained attapulgite-titanium dioxide composite material is uniformly distributed on the surface of the attapulgite, and meanwhile, the attapulgite in the composite material still maintains low agglomeration.

Description

Method for uniformly preparing attapulgite-titanium dioxide composite material
Technical Field
The invention relates to the technical field of hybrid materials, in particular to a method for uniformly preparing an attapulgite-titanium dioxide composite material.
Background
Attapulgite (ATP) is a natural nanoscale mineral material with special rod-like fiber structure, and its ideal molecular formula is Mg5(H2O)4[Si4O10](OH)2The crystal structure is a channel type crystal structure formed by connecting two silicon-oxygen tetrahedrons with an aluminum-oxygen tetrahedron sandwiched therebetween through oxygen. The attapulgite has a special chain lamellar crystal structure and good colloidal properties of dispersion, water absorption, salt and alkali resistance and the like, and has good catalytic and heat resistance properties due to the nanometer-scale pore canals and fine crystal sizes.
Titanium dioxide is a white solid or powdery amphoteric oxide, has good opacity and smoothness, and has the advantages of no toxicity, no irritation, no volatilization, good thermal stability, rich resources and the like. The titanium dioxide has three crystal forms of anatase, rutile and brookite, the formation of the crystal structure is mainly related to the temperature, the anatase structure can be obtained by calcining at 500 ℃, the calcining temperature is higher than 800 ℃, the rutile structure with higher purity can be obtained, and meanwhile, the deformation capacity of the anatase crystal form is higher than that of the rutile crystal form. Preparation of titanium dioxide (ATP-TiO) loaded on surface of attapulgite2) The hybrid material simultaneously utilizes the high specific surface area of the attapulgite and the photocatalytic characteristic and the resistance of the titanium dioxideThe hybrid material can be used in the fields of adsorption, photocatalysis and the like, and shows excellent adsorption and photocatalysis performance.
Preparation of ATP-TiO at present2The method mainly comprises 1) a sol-gel method, for example, in the patent 'a method for preparing a nano titanium dioxide/attapulgite composite material (CN 101333345A)', attapulgite is dispersed into deionized water to prepare slurry, then attapulgite slurry is added into a nano titanium dioxide precursor to form nano titanium dioxide/attapulgite composite particles, and then the nano titanium dioxide/attapulgite composite material powder is prepared by using an alkaline solution to adjust the pH value, filtering and washing, drying a filter cake and the like. 2) Acid-base neutralization cocurrent flow method: preparing acidic titanium dioxide sol from titanium tetrachloride by using dilute hydrochloric acid, aging for later use, adding the modified attapulgite powder into water to prepare aqueous suspension, adjusting the pH value to be alkaline, uniformly mixing the aqueous suspension with the acidic titanium dioxide sol in a certain ratio, reacting at 70 ℃, washing and calcining to obtain a microstructure [ J ] of a powder (Zhao Fang, Zhou Jie, Liu Ning, copper modified attapulgite/nano titanium dioxide composite powder]Silicate school, 2006,34(007): 792-795). 3) The dipping method comprises the following steps: XieJing crystal (Mianshuan, XieJing crystal, Qingchengsong, etc.. carrying TiO)2Method for treating acid fuchsin dye wastewater by attapulgite photocatalytic oxidation method]Silicate science 2006,34(11):1208- & 1212) preparation of supported TiO by impregnation2Attapulgite, which is prepared by the following steps: dipping the pretreated attapulgite powder into a butyl titanate ethanol solution, stirring uniformly, and washing away the free butyl titanate on the surface of the attapulgite by using ethanol; placing the attapulgite adsorbed with the butyl titanate in a crucible, placing the crucible in a beaker filled with a small amount of water, sealing the beaker, placing the beaker in an oven, heating at 60-80 ℃, hydrolyzing the butyl titanate on the surface of the beaker to form titanium hydroxide, and calcining and grinding the product to obtain the titanium dioxide/attapulgite composite material. 4) Ultrasonic dispersion-reprecipitation method (preparation, modification and photocatalytic performance research of Anqingzhen nano titanium dioxide [ D)]University of north and river, 2011.): dispersing attapulgite in TiOSO4Adding an alkali solution into the precursor solution after ultrasonic dispersion; adding a certain amount of filter cake obtained after the precipitate is filtered and washed for multiple timesDiluting with ionized water, hydrolyzing at a certain temperature, filtering, washing, drying and calcining the obtained product to obtain attapulgite/TiO2A composite material.
Aiming at the titanium dioxide hybrid material loaded on the surface of the attapulgite, the biggest problems exist at present in how to improve the dispersion degree of attapulgite bundles and how to control the distribution uniformity during the synthesis of the titanium dioxide. The sol-gel method, the acid-base neutralization parallel flow method and the ultrasonic dispersion-reprecipitation method which are commonly used at present have the problems that the loading capacity (namely the uniformity) of titanium dioxide on the surface of attapulgite cannot be controlled, excessive precursors can be hydrolyzed to generate self-agglomeration at the stage of hydrolyzing the precursors to generate titanium hydroxide, the attapulgite is completely wrapped to form micron-sized particles, and the advantages and the effects of nano materials cannot be exerted (from Anqingzhen: the preparation and modification of nano titanium dioxide and the research on photocatalytic performance, Anqingzhen. the preparation and modification of nano titanium dioxide and the research on photocatalytic performance [ D ]. Hebei university, 2011.). The impregnation method improves the control problem of the precursor content in the hybrid material synthesis process, and the adopted method comprises the steps of dispersing the attapulgite in a butyl titanate precursor solution, washing off redundant butyl titanate by using ethanol, and slowly hydrolyzing the butyl titanate on the surface of the impregnated attapulgite by using a steam method. The method can effectively improve the condition of titanium dioxide agglomeration caused by excessive hydrolysis of butyl titanate, but the titanium dioxide on the surface of the attapulgite is still not uniformly distributed.
Disclosure of Invention
The invention aims to provide a method for uniformly preparing an attapulgite-titanium dioxide composite material, wherein titanium dioxide in the prepared attapulgite-titanium dioxide composite material is uniformly distributed on the surface of the attapulgite.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for uniformly preparing an attapulgite-titanium dioxide composite material, which comprises the following steps:
1) pretreating attapulgite to obtain purified attapulgite;
2) mixing butyl titanate, ethanol and acid to obtain a butyl titanate precursor solution;
3) mixing the purified attapulgite and a butyl titanate precursor solution, carrying out suction filtration, adding ethanol into the obtained solid product, and sequentially and alternately carrying out stirring and ultrasonic dispersion until the obtained dispersion liquid is viscous and does not settle to obtain an attapulgite-butyl titanate precursor dispersion liquid;
4) carrying out steam hydrolysis on the attapulgite-tetrabutyl titanate precursor dispersion liquid under the conditions of magnetic stirring and constant-temperature water bath, and sequentially aging, drying and calcining the obtained product to obtain an attapulgite-titanium dioxide composite material;
the rotating speed of the magnetic stirring is 80-240 rpm, and the temperature of the constant-temperature water bath is 40-60 ℃;
step 1) and step 2) are not limited in chronological order.
Preferably, the pretreatment in step 1) comprises the following steps: mixing attapulgite with water to obtain a suspension; and adjusting the pH value of the suspension to 9-11, and sequentially aging, stirring, dispersing, drying and grinding to obtain the purified attapulgite.
Preferably, the aging time is 12-24 h; the stirring and dispersing time is 4-6 h; the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
Preferably, in the step 2), the volume ratio of the butyl titanate to the ethanol is 1 (3-4); the volume ratio of the butyl titanate to the acid is 1 (0.2-0.3).
Preferably, the dosage ratio of the purified attapulgite to the butyl titanate is 1g (5-10) mL.
Preferably, in the step 3), the mixing process of the purified attapulgite and the butyl titanate precursor solution comprises stirring and ultrasonic dispersion which are sequentially carried out, wherein the stirring time is 1-3 hours, and the ultrasonic dispersion time is 1-3 hours.
Preferably, in the step 3), the using amount ratio of the ethanol to the purified attapulgite is (6-10) mL: 2g of the total weight.
Preferably, in the step 4), the aging time is 12-24 hours.
Preferably, in the step 4), the drying temperature is 60-80 ℃ and the time is 12 hours.
Preferably, in the step 4), the calcining temperature is 500-550 ℃, and the heat preservation time is 120-240 min; the heating rate of the temperature rising to the calcining temperature is 2-4 ℃/min.
The invention provides a method for uniformly preparing an attapulgite-titanium dioxide composite material, which comprises the following steps: 1) pretreating attapulgite to obtain purified attapulgite; 2) mixing butyl titanate, ethanol and acetic acid to obtain a butyl titanate precursor solution; 3) mixing the purified attapulgite and a butyl titanate precursor solution, carrying out suction filtration, adding ethanol into the obtained solid product, and sequentially and alternately carrying out stirring and ultrasonic dispersion until the obtained dispersion liquid is viscous and does not settle to obtain an attapulgite-butyl titanate precursor dispersion liquid; 4) carrying out steam hydrolysis on the attapulgite-tetrabutyl titanate precursor dispersion liquid under the conditions of magnetic stirring and constant-temperature water bath, and sequentially aging, drying and calcining the obtained product to obtain an attapulgite-titanium dioxide composite material; the rotating speed of the magnetic stirring is 80-240 rpm, and the temperature of the constant-temperature water bath is 40-60 ℃; step 1) and step 2) are not limited in chronological order. The method adopts a steam hydrolysis method, magnetic stirring is assisted in the whole hydrolysis process, hydrolysis is carried out by a water bath constant temperature heating method, and the stirring speed and the water bath temperature are controlled simultaneously, so that the contact speed of the attapulgite and water vapor and the hydrolysis degree of butyl titanate are controlled, the uniformity of titanium dioxide can be ensured, the titanium dioxide in the obtained attapulgite-titanium dioxide composite material is uniformly distributed on the surface of the attapulgite, and meanwhile, the attapulgite in the composite material still maintains low agglomeration property after pretreatment.
Drawings
FIG. 1 is a schematic diagram of a steam hydrolysis reaction according to the present invention;
FIG. 2 is an FESEM image and a TEM image of pure attapulgite and the attapulgite-titanium dioxide composite materials prepared in examples 1-3 and comparative example 1;
FIG. 3 is an XRD (X-ray diffraction) pattern of pure attapulgite, pure titanium dioxide and the attapulgite-titanium dioxide composite materials prepared in examples 1-3 and comparative example 1;
FIG. 4 is a graph showing the thermogravimetry of pure attapulgite, pure titanium dioxide and the attapulgite-titanium dioxide composite materials prepared in examples 1-3 and comparative example 1;
FIG. 5 is a mapping chart of the attapulgite-titania composite prepared in example 3.
Detailed Description
The invention provides a method for uniformly preparing an attapulgite-titanium dioxide composite material, which comprises the following steps:
1) pretreating attapulgite to obtain purified attapulgite;
2) mixing butyl titanate, ethanol and acid to obtain a butyl titanate precursor solution;
3) mixing the purified attapulgite and a butyl titanate precursor solution, carrying out suction filtration, adding ethanol into the obtained solid product, and sequentially and alternately carrying out stirring and ultrasonic dispersion until the obtained dispersion liquid is viscous and does not settle to obtain an attapulgite-butyl titanate precursor dispersion liquid;
4) carrying out steam hydrolysis on the attapulgite-tetrabutyl titanate precursor dispersion liquid under the conditions of magnetic stirring and constant-temperature water bath, and sequentially aging, drying and calcining the obtained product to obtain an attapulgite-titanium dioxide composite material;
the rotating speed of the magnetic stirring is 80-240 rpm, and the temperature of the constant-temperature water bath is 40-60 ℃;
step 1) and step 2) are not limited in chronological order.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention pretreats the attapulgite to obtain the purified attapulgite. In the present invention, the pretreatment preferably comprises the steps of: mixing attapulgite with water to obtain a suspension; and adjusting the pH value of the suspension to 9-11, and sequentially aging, stirring, dispersing, drying and grinding to obtain the purified attapulgite. In the present invention, before mixing the attapulgite with water, the attapulgite is preferably ground to 200 mesh or less. The process for mixing the attapulgite and the water is not particularly limited, and the raw materials can be uniformly mixed according to the process well known in the art. In the invention, the mass concentration of the suspension is preferably 5-10%, and more preferably 6-8%.
The process of adjusting the pH of the suspension according to the present invention is not particularly limited, and the above pH conditions can be achieved according to the processes well known in the art. In the invention, the aging time is preferably 12-24 h, and more preferably 16-20 h; the temperature is preferably 20-25 ℃; the invention leads colloidal particles in the suspension to be aggregated to form gel with a network structure by aging.
In the invention, the stirring and dispersing time is preferably 4-6 h, and more preferably 5 h; the rotating speed of stirring and dispersing is preferably 160-240 rpm, and more preferably 180-200 rpm; the drying temperature is preferably 60-80 ℃, more preferably 65-75 ℃, and the time is preferably 12-24 hours, more preferably 16-20 hours. After the drying is finished, the obtained dried material is preferably ground and sieved by a 400-mesh sieve, so that the purified attapulgite is obtained. The invention removes impurities such as gravel and the like in the attapulgite through pretreatment.
The method mixes butyl titanate, ethanol and acid to obtain the butyl titanate precursor solution. In the present invention, the acid is preferably acetic acid, hydrochloric acid or nitric acid; the concentration of the acid is not particularly limited in the present invention, and commercially available ones well known in the art may be used. In the invention, the volume ratio of the butyl titanate to the ethanol is preferably 1 (3-4), and more preferably 1 (3.2-3.6); the volume ratio of the butyl titanate to the acid is preferably 1 (0.2-0.3), and more preferably 1: 0.25. In the invention, the process of mixing the butyl titanate, the ethanol and the acid is preferably to prepare the butyl titanate and the ethanol into a solution, add the acid, and magnetically stir the obtained solution for 20-60 min; the rotation speed of the magnetic stirring is not particularly limited, and a uniform butyl titanate precursor solution can be obtained, specifically 320rpm or 480rpm in the embodiment of the invention. The invention utilizes acid to prevent the butyl titanate from hydrolysis reaction in advance.
After obtaining the butyl titanate precursor solution, mixing the purified attapulgite with the butyl titanate precursor solution, carrying out suction filtration, adding ethanol into the obtained solid product, and sequentially and alternately carrying out stirring and ultrasonic dispersion until the obtained dispersion liquid is in a viscous and non-settling state, thereby obtaining the attapulgite-butyl titanate precursor dispersion liquid. In the invention, the dosage ratio of the purified attapulgite to the butyl titanate is preferably 1g (5-10) mL, and more preferably 1g (6-8) mL.
In the invention, the process of mixing the purified attapulgite and the butyl titanate precursor solution preferably comprises stirring and ultrasonic dispersion which are sequentially carried out, the stirring time is preferably 1-3 h, more preferably 2h, and the stirring rotating speed is preferably 300-600 rpm, more preferably 400-500 rpm; the time for ultrasonic dispersion is preferably 1-3 h, and more preferably 2 h. The invention utilizes the stirring process to ensure that the purified attapulgite adsorbs the butyl titanate precursor, and ensures that the attapulgite can not be agglomerated in a large amount through ultrasonic dispersion.
After the mixing is finished, the obtained material is preferably subjected to suction filtration to remove excessive butyl titanate ethanol solution; the process of the suction filtration is not particularly limited in the present invention, and may be carried out according to a process known in the art.
After the suction filtration is finished, adding ethanol into the obtained product, and sequentially and alternately stirring and ultrasonically dispersing until the obtained dispersion liquid is in a viscous and non-settling state to obtain the attapulgite-butyl titanate precursor dispersion liquid. In the invention, the preferable dosage ratio of the ethanol to the purified attapulgite is (6-10) mL: 2g, more preferably (7-8) mL: 2g of the total weight. In the invention, in the process of alternately stirring and ultrasonically dispersing, the rotation speed of each stirring is preferably 300-600 rpm, more preferably 400-500 rpm, and the time is preferably 3-5 h, more preferably 3.5-4.5 h; the time of each ultrasonic dispersion is preferably 3-5 h, and more preferably 3.5-4.5 h. According to the invention, the ethanol is adopted to wash off the redundant butyl titanate precursor, so that the redundant titanium dioxide aggregate can not be generated in the composite material. The attapulgite-tetrabutyl titanate precursor dispersion liquid keeps a viscous and non-settling state by alternately stirring and ultrasonically dispersing, can prevent the agglomeration of the attapulgite, and is beneficial to the uniform distribution of titanium dioxide on the surface of the attapulgite.
After the attapulgite-tetrabutyl titanate precursor dispersion liquid is obtained, carrying out steam hydrolysis on the attapulgite-tetrabutyl titanate precursor dispersion liquid under the conditions of magnetic stirring and constant-temperature water bath, and sequentially aging, drying and calcining the obtained product to obtain an attapulgite-titanium dioxide composite material; the rotation speed of the magnetic stirring is 80-240 rpm, and the temperature of the constant-temperature water bath is 40-60 ℃.
In the present invention, the container containing the attapulgite-tetrabutyl titanate precursor dispersion liquid is preferably sealed by using a preservative film, and then placed in a water bath for steam hydrolysis (as shown in fig. 1). In the invention, the rotation speed of the magnetic stirring is 80-240 rpm, preferably 100-200 rpm, and more preferably 150 rpm. In the invention, the temperature of the steam hydrolysis is 40-60 ℃, preferably 45-55 ℃, and more preferably 50 ℃; the reaction completion point of the steam hydrolysis is based on complete sol; the complete solation can be distinguished according to criteria well known in the art.
In the steam hydrolysis process, a water bath is used for providing a constant temperature environment, so that the deionized water is slowly evaporated at a low temperature; the attapulgite-tetrabutyl titanate precursor dispersion liquid is uniformly contacted with the water vapor by magnetic stirring, so that the hydrolysis process is more complete.
In the steam hydrolysis process, in the attapulgite-butyl titanate precursor dispersion liquid, sufficient butyl titanate is adsorbed on the surface of attapulgite, and is hydrolyzed after reacting with water vapor, and the specific reaction process is as follows:
Ti(OR)4+4H2O→Ti(OH)4+4ROH；
Ti(OH)4+Ti(OR)4→2TiO2+4ROH；
2Ti(OH)4→2TiO2+4H2O
the invention controls the saturated vapor pressure of water by controlling the temperature of the water bath, realizes the slow evaporation of water, and is easier to control the hydrolysis speed of hydrolysis reaction compared with the method of directly dripping deionized water in the original sol-gel method, thereby controlling the hydrolysis degree of the butyl titanate and ensuring the uniformity of the titanium dioxide. According to the invention, in the hydrolysis process, the contact speed of the attapulgite and the water vapor is controlled by using magnetic stirring, so that the whole hydrolysis process is carried out in a dynamic environment on the basis of not damaging a gel structure, the attapulgite is uniformly contacted with the water vapor, and the uniform distribution of titanium dioxide on the surface of the attapulgite is realized.
After the steam hydrolysis is finished, the obtained product is aged, dried and calcined in sequence to obtain the attapulgite-titanium dioxide composite material. In the invention, the aging time is preferably 12-24 h, and more preferably 15-20 h; the temperature is preferably 20-25 ℃. The invention makes the product colloid particles obtained by steam hydrolysis aggregate to form network structure gel through aging.
In the invention, the drying temperature is preferably 60-80 ℃, more preferably 65-75 ℃, and the time is preferably 12 h. In the invention, the calcination is preferably carried out in a muffle furnace, the calcination temperature is preferably 500-550 ℃, more preferably 520-530 ℃, and the heat preservation time is preferably 120-240 min, more preferably 150-200 min; the heating rate of the temperature to the calcining temperature is preferably 2-4 ℃/min, and more preferably 3 ℃/min. According to the invention, the crystal structure of titanium dioxide is controlled to be an anatase structure through calcination, so that the generation of brookite type titanium dioxide with a loose and unstable structure is avoided.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The attapulgite used in the following examples is purified attapulgite pretreated according to the following steps: grinding attapulgite to below 200 meshes, preparing a suspension with the mass concentration of 5% by using distilled water, adjusting the pH value of the suspension to 11, aging at 25 ℃ for 24h, magnetically stirring and dispersing for 4h (240rpm), drying at 60 ℃ for 12h, grinding and sieving by using a 400-mesh sieve to obtain the purified attapulgite.
Example 1
Mixing 10mL of butyl titanate with 30mL of ethanol, adding 2mL of acetic acid, and magnetically stirring the obtained solution for 30min (the rotating speed is 480rpm) to obtain a butyl titanate precursor solution;
adding 2g of purified attapulgite into the tetrabutyl titanate precursor solution, performing magnetic stirring for 2 hours (the rotating speed is 320rpm), performing ultrasonic dispersion for 1 hour, performing suction filtration, adding 10mL of ethanol into the obtained product, and sequentially and alternately performing stirring (30min, 480rpm) and ultrasonic dispersion (30min) for three times respectively to obtain an attapulgite-tetrabutyl titanate precursor dispersion liquid;
putting the attapulgite-tetrabutyl titanate precursor dispersion liquid into a small beaker (100mL), putting the small beaker into a large beaker (500mL), adding 100mL of deionized water at the periphery, sealing the large beaker by using a preservative film, putting the large beaker into a water bath kettle, magnetically stirring, heating at the constant temperature of 60 ℃ at the rotating speed of 80rpm, carrying out steam hydrolysis, finishing the reaction, aging the obtained product at 25 ℃ for 12 hours, drying in a 60 ℃ oven for 12 hours, calcining at 510 ℃, grinding the calcined product and sieving with a 400-mesh sieve to obtain the attapulgite-titanium dioxide composite material.
Example 2
Mixing 10mL of butyl titanate with 40mL of ethanol, adding 2mL of acetic acid, and magnetically stirring the obtained solution for 20min (the rotating speed is 320rpm) to obtain a butyl titanate precursor solution;
adding 2g of purified attapulgite into the tetrabutyl titanate precursor solution, performing magnetic stirring for 2 hours (the rotating speed is 320rpm), performing ultrasonic dispersion for 1 hour, performing suction filtration, adding 10mL of ethanol into the obtained product, and sequentially and alternately performing stirring (30min, 320rpm) and ultrasonic dispersion (30min) for three times respectively to obtain an attapulgite-tetrabutyl titanate precursor dispersion liquid;
putting the attapulgite-tetrabutyl titanate precursor dispersion liquid into a small beaker (100mL), putting the small beaker into a large beaker (500mL), adding 100mL of deionized water at the periphery, sealing the large beaker by using a preservative film, putting the large beaker into a water bath kettle, magnetically stirring, heating at constant temperature of 40 ℃ at a rotating speed of 160rpm, carrying out steam hydrolysis, finishing the reaction, aging the obtained product at 25 ℃ for 12 hours, drying in a 60 ℃ oven for 12 hours, calcining at 550 ℃, grinding the calcined product and sieving with a 400-mesh sieve to obtain the attapulgite-titanium dioxide composite material.
Example 3
Mixing 75mL of butyl titanate with 225mL of ethanol, adding 15mL of acetic acid, and magnetically stirring the obtained solution for 60min (the rotating speed is 480rpm) to obtain a butyl titanate precursor solution;
adding 15g of purified attapulgite into the tetrabutyl titanate precursor solution, performing magnetic stirring for 3 hours (the rotating speed is 480rpm), performing ultrasonic dispersion for 3 hours, performing suction filtration, adding 50mL of ethanol into the obtained product, and sequentially and alternately performing stirring (30min, 480rpm) and ultrasonic dispersion (30min) for three times respectively to obtain an attapulgite-tetrabutyl titanate precursor dispersion liquid;
putting the attapulgite-tetrabutyl titanate precursor dispersion liquid into a small beaker (100mL), putting the small beaker into a large beaker (500mL), adding 100mL of deionized water at the periphery, sealing the large beaker by using a preservative film, putting the large beaker into a water bath kettle, magnetically stirring, heating at the constant temperature of 60 ℃ at the rotating speed of 240rpm, carrying out steam hydrolysis, finishing the reaction, aging the obtained product at 25 ℃ for 12 hours, drying in a 60 ℃ oven for 24 hours, calcining at 510 ℃, grinding the calcined product and sieving with a 400-mesh sieve to obtain the attapulgite-titanium dioxide composite material.
Comparative example 1
Mixing 10mL of butyl titanate with 30mL of ethanol, adding 2mL of acetic acid, and magnetically stirring the obtained solution for 30min (480rpm) to obtain a butyl titanate precursor solution;
adding 2g of purified attapulgite into the tetrabutyl titanate precursor solution, performing magnetic stirring for 2 hours (the rotating speed is 320rpm), performing ultrasonic dispersion for 1 hour, performing suction filtration, adding 10mL of ethanol into the obtained product, and sequentially and alternately performing stirring (30min, 480rpm) and ultrasonic dispersion (30min) for three times respectively to obtain an attapulgite-tetrabutyl titanate precursor dispersion liquid;
putting the attapulgite-tetrabutyl titanate precursor dispersion liquid into a small beaker (100mL), putting the small beaker into a large beaker (500mL), adding 100mL of deionized water at the periphery, sealing the large beaker by using a preservative film, putting the large beaker into a water bath kettle for standing, heating at the constant temperature of 60 ℃, carrying out steam hydrolysis, aging the obtained product at 25 ℃ for 12 hours after the reaction is finished, drying in a 60 ℃ oven for 12 hours, calcining at 510 ℃, grinding the calcined product and sieving with a 400-mesh sieve to obtain the attapulgite-titanium dioxide composite material.
Performance testing
1) The attapulgite-titania composites prepared in examples 1 to 3 and comparative example 1 were subjected to FESEM and TEM tests, while pure Attapulgite (ATP) was used as a comparison, and the results are shown in FIG. 2, wherein (a), (c), (e), (g) and (i) are FESEM images, and (b), (d), (f), (h) and (j) are TEM images. As can be seen from FIG. 2, the pure attapulgite has smooth surface and exists in bundles. The titanium dioxide loading capacity of the surface of the attapulgite prepared by the comparative example 1 (standing hydrolysis condition) is less, and the loading position is loose; the titanium dioxide loaded on the surface of the attapulgite prepared by hydrolyzing under the magnetic stirring condition in the embodiments 1-3 is increased, and in the morphology of the embodiment 3 (shown in (g) and (h) in fig. 2), the attapulgite is loaded most and most densely, meanwhile, the diameter of the attapulgite is increased, and rod crystals are clustered, which shows that the loading and uniformity of the titanium dioxide on the surface of the attapulgite are influenced by the speed of the magnetic stirring in the hydrolysis process.
2) XRD (X-ray diffraction) tests were performed on the attapulgite-titanium dioxide composite materials prepared in examples 1-3 and comparative example 1, and the results are shown in figure 3, wherein pure attapulgite (primary ATP) and pure titanium dioxide are used as comparison. As can be seen from FIG. 3, the pure attapulgite shows characteristic diffraction peaks of its crystal structure at 2 θ of 16.28 °, 19.82 °, 20.74 °, 27.38 ° and 35.10 °. For pure TiO2Wherein the diffraction angles 2 theta are 25.3 degrees, 38.3 degrees, 48.2 degrees, 54.5 degrees and 62.5 degrees which belong to the (101), (004), (200), (105 and 211) and (204) crystal face diffraction of anatase phase respectively, and the diffraction characteristics of a small amount of rutile are shown, which indicates that the main component of titanium dioxide is anatase phase with stable structure under the calcination of 510-550 ℃. Observing the XRD characteristic spectrum of the attapulgite-titanium dioxide composite material, finding and comparingThe attapulgite-titania composite material prepared in example 1 (under the standing condition) retained most of the peaks characteristic to attapulgite, because the amount of titania supported was small at this content, and it can be seen from the transmission electron microscope spectrum (as shown in i in fig. 2) of comparative example 1 that the titania particle size under this condition was small and the distribution was loose on the surface of attapulgite, presumably because the peaks characteristic to titania were less apparent. Under the condition of magnetic stirring (in examples 1 to 3), the attapulgite-titanium dioxide composite material has an obvious characteristic peak of titanium dioxide, and the characteristic peak of the attapulgite is covered. Comparing the spectrogram of the example 1-3 with the spectrogram of pure titanium dioxide, the finding that the titanium dioxide in the attapulgite-titanium dioxide composite filler is mainly anatase phase shows that the method successfully loads the titanium dioxide on the surface of the attapulgite.
3) The attapulgite-titanium dioxide composite materials prepared in examples 1-3 and comparative example 1 were subjected to a thermal weight loss test, and pure attapulgite (primary ATP) and pure titanium dioxide were used as a comparison, and the results are shown in fig. 4, where the right side is a partially enlarged view of the curve in the square frame, and as can be seen from fig. 4, pure titanium dioxide hardly has mass loss in the temperature range from room temperature to 800 ℃, and the mass loss of pure attapulgite is large. After the titanium dioxide is loaded on the surface of the attapulgite, the addition of the titanium dioxide ensures that the overall heat resistance of the composite material is obviously improved compared with that of the pure attapulgite; by comparing the mass loss of the attapulgite and the composite filler, the mass ratio of the attapulgite to the titanium dioxide loaded on the surface thereof under standing (comparative example 1) and magnetic stirring (examples 1-3) can be obtained, as shown in table 1.
TABLE 1 Mass ratio of Attapulgite-Titania composites prepared in examples 1-3 and comparative example 1
Figure BDA0002731309100000111
As can be seen from Table 1, the amount of titanium dioxide loaded in the attapulgite-titanium dioxide composite material obtained under magnetic stirring (examples 1 to 3) was higher than that in comparative example 1 (under standing condition).
4) The attapulgite-titanium dioxide composite material prepared in example 3 was subjected to element distribution characterization, and the results are shown in fig. 5. As can be seen from FIG. 5, O, Ti and Si elements can be detected on the surface of the attapulgite-titanium dioxide composite material, and meanwhile, the element distribution area is observed, so that the titanium element distribution area is larger than that of the silicon element, and the titanium element is uniformly distributed, which indicates that titanium dioxide particles are uniformly loaded on the surface of the attapulgite.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (1)

1. A method for uniformly preparing an attapulgite-titanium dioxide composite material comprises the following steps:
mixing 75mL of butyl titanate with 225mL of ethanol, adding 15mL of acetic acid, and magnetically stirring the obtained solution for 60min at the rotating speed of 480rpm to obtain a butyl titanate precursor solution;
adding 15g of purified attapulgite into the butyl titanate precursor solution, magnetically stirring for 3h, performing ultrasonic dispersion for 3h at the rotating speed of 480rpm, performing suction filtration, adding 50mL of ethanol into the obtained product, and sequentially and alternately stirring and performing ultrasonic dispersion for 30min three times respectively at the rotating speed of 480rpm to obtain an attapulgite-butyl titanate precursor dispersion liquid;
putting the attapulgite-tetrabutyl titanate precursor dispersion liquid into a 100mL beaker, putting the beaker into a 500mL big beaker, adding 100mL deionized water at the periphery, sealing the big beaker by using a preservative film, putting the beaker into a water bath kettle, magnetically stirring, heating at the constant temperature of 240rpm and 60 ℃, carrying out steam hydrolysis, aging the obtained product at 25 ℃ for 12 hours after the reaction is finished, drying in a 60 ℃ oven for 24 hours, calcining at 510 ℃, grinding the calcined product and sieving with a 400-mesh sieve to obtain the attapulgite-titanium dioxide composite material.
CN202011118901.2A 2020-10-19 2020-10-19 Method for uniformly preparing attapulgite-titanium dioxide composite material Active CN112108137B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011118901.2A CN112108137B (en) 2020-10-19 2020-10-19 Method for uniformly preparing attapulgite-titanium dioxide composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011118901.2A CN112108137B (en) 2020-10-19 2020-10-19 Method for uniformly preparing attapulgite-titanium dioxide composite material

Publications (2)

Publication Number Publication Date
CN112108137A CN112108137A (en) 2020-12-22
CN112108137B true CN112108137B (en) 2022-05-27

Family

ID=73794195

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011118901.2A Active CN112108137B (en) 2020-10-19 2020-10-19 Method for uniformly preparing attapulgite-titanium dioxide composite material

Country Status (1)

Country Link
CN (1) CN112108137B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214538B (en) * 2021-04-21 2022-05-20 安徽江淮汽车集团股份有限公司 Thermoplastic resin filler, preparation method thereof and thermoplastic resin composite material
CN114410095B (en) * 2021-12-31 2023-02-03 江苏常阳科技有限公司 Sheet molding compound for adsorbing and degrading formaldehyde and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303904B (en) * 2011-08-11 2013-06-05 四川龙蟒钛业股份有限公司 Hydrolysis method for preparing high-brightness rutile titanium white from low-concentration titaniferous solution
CN105597718A (en) * 2015-10-12 2016-05-25 福建师范大学泉港石化研究院 Preparation method of inorganic mineral powder supported nano-TiO2 photocatalyst
CN108878831A (en) * 2018-06-27 2018-11-23 深圳大学 A method of improving silicon based anode material electric conductivity

Also Published As

Publication number Publication date
CN112108137A (en) 2020-12-22

Similar Documents

Publication Publication Date Title
Zou et al. Facile preparation and photocatalytic activity of oxygen vacancy rich BiOCl with {0 0 1} exposed reactive facets
Wei et al. Tricomponent brookite/anatase TiO 2/gC 3 N 4 heterojunction in mesoporous hollow microspheres for enhanced visible-light photocatalysis
CN112108137B (en) Method for uniformly preparing attapulgite-titanium dioxide composite material
Kimling et al. Sol–gel synthesis of hierarchically porous TiO 2 beads using calcium alginate beads as sacrificial templates
CN104759261B (en) A kind of titanic oxide nano compound material and its production and use
CN106475127A (en) A kind of nitrogen-doped graphene quantum dot/mesopore titania photocatalyst and preparation method thereof
Moongraksathum et al. CeO 2–TiO 2 mixed oxide thin films with enhanced photocatalytic degradation of organic pollutants
CN101318126B (en) Method of preparing high-degree of crystallinity, large-specific surface area nano-titanium dioxide photocatalyst
Dahl et al. Control of the crystallinity in TiO 2 microspheres through silica impregnation
CN112588283A (en) Carbon quantum dot/mesoporous layered titanium dioxide and preparation method and application thereof
Neale et al. Size and shape control of nanocrystallites in mesoporous TiO 2 films
CN113333023B (en) High-adsorption bismuth oxyiodide visible-light-driven photocatalyst and application thereof
CN105158295A (en) Preparation method of titanium dioxide-graphene composite humidity-sensitive material
CN1108276C (en) Process for preparing boehmite ultrafine nanometer powder
Feng et al. Preparation of novel porous hydroxyapatite sheets with high Pb2+ adsorption properties by self-assembly non-aqueous precipitation method
CN1915836A (en) Method for preparting Nano powder of zirconia
Yang et al. Single-step preparation, characterization and photocatalytic mechanism of mesoporous Fe-doped sulfated titania
CN113860341A (en) High-purity flaky boehmite and preparation method thereof
CN110586058B (en) Preparation method of nano titanium dioxide/zirconium oxide composite photocatalyst
CN104909405A (en) Cellulose-based template based spindle-shaped nano-titanium dioxide and preparation method thereof
CN110743522B (en) High-index crystal face titanium dioxide nano catalyst and preparation method thereof
CN109999774B (en) Preparation method of nano titanium dioxide/gamma-alumina composite material powder
CN106829926A (en) A kind of high-purity spiral carbon nanotubes and preparation method thereof
CN113877515B (en) Eighteen-surface lanthanum ferrite adsorbent and preparation method thereof
CN109775756A (en) A kind of synthetic method of high thermal stability rutile titania phase nano-titanium dioxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant