CN108212108A - A kind of recessed native composite adsorbing material and preparation method - Google Patents

A kind of recessed native composite adsorbing material and preparation method Download PDF

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CN108212108A
CN108212108A CN201810076716.8A CN201810076716A CN108212108A CN 108212108 A CN108212108 A CN 108212108A CN 201810076716 A CN201810076716 A CN 201810076716A CN 108212108 A CN108212108 A CN 108212108A
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chitosan
recessed soil
composite material
attapulgite
recessed
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CN108212108B (en
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谭凯婷
王志红
谭婉玲
聂锦旭
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Guangdong University of Technology
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Guangdong University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/165Natural alumino-silicates, e.g. zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The present invention provides a kind of attapulgite composite material, including being acidified recessed soil and being supported on the chitosan and titanium dioxide that are acidified on recessed soil;The chitosan is 1 with the mass ratio for being acidified recessed soil:(50~200).The present invention is by TiO2, CTS be carried on the carrier of recessed this high-specific surface area of soil, TiO is effectively prevented for carrier with recessed soil2Agglomeration, and the load of chitosan be TiO2Provide more attachment sites so that particle is more dispersed, uniform.Modified recessed soil structure is changed into cellular, specific surface area increase by sheet, and surface amino groups and hydroxyl quantity increase, and enhance the absorption property of recessed soil.The experimental results showed that the attapulgite composite material in the present invention all has effect of the removal rate stabilization 90% to pollutant humic acid common in water process, Congo red, Cr (VI).The present invention also provides a kind of preparation methods of attapulgite composite material.

Description

A kind of recessed native composite adsorbing material and preparation method
Technical field
The invention belongs to water-treatment technology fields more particularly to a kind of recessed native composite adsorbing material and preparation method thereof.
Background technology
Recessed soil (abbreviation ATP) is a kind of crystalloid hydration alumina magnesia silicate, has extremely strong hydrophily.Recessed soil application When wastewater treatment, the reason of adsorption capacity is restricted, is mainly reflected at following 2 points:First, when water and organic pollution In recessed native apparent competitive absorption, hydrone is preferentially adsorbed, and is occupied the activated adoption site of recessed native channel surfaces, is made its right Organic pollutant removal rate reduces;Second is that recessed soil surface can be high, it is caused easily to assemble agglomerating, specific surface area is reduced.Cause This, the recessed soil of natural output generally can not meet the requirement of water process organics removal.
Physical or chemical modification is carried out to recessed soil and has a large amount of research in water treatment field, in order to improve pollutant Removal rate reduces dosage and reduces the secondary pollution caused by environment as far as possible, scholar to the method for recessed land reform and The initial solubility of dosage, pH value of solution, solution of modified material and reaction time etc. are right to being studied in the influence of adsorption effect Industrial applications are attempted.
In existing recessed native modification technology, the absorption property of recessed soil utilizes abundant not enough, when handling organic wastewater, There are the problems such as removal rate is not high, the reaction time is longer, applicable pH range is small.
Invention content
The purpose of the present invention is to provide a kind of attapulgite composite material and preparation method thereof, the recessed native composite wood in the present invention Material adsorption efficiency is high, be swift in response, resistance to acid and alkali is strong.
The present invention provides a kind of attapulgite composite material, including being acidified recessed soil and being supported on the chitosan and two being acidified on recessed soil Titanium oxide;
The chitosan is 1 with the mass ratio for being acidified recessed soil:(50~200);
Preferably, the attapulgite composite material is porous structure;
The aperture of the attapulgite composite material is 100~150nm.
The grain size of the attapulgite composite material is 1~5 μm.
The present invention provides a kind of preparation method of attapulgite composite material, includes the following steps:
A) recessed soil with hydrochloric acid solution is mixed, suspension is centrifuged and dried, obtains being acidified recessed soil;
B) the recessed soil of the acidification is added in chitosan solution, bumps are modified, is then centrifuged and is dried, are obtained To chitosan/attapulgite material;
C) chitosan/attapulgite material is added in the ethanol solution of butyl titanate, then adds in absolute ethyl alcohol, nitre The mixed solution of acid and water is dried after forming colloidal sol, obtains attapulgite composite material.
Preferably, a concentration of 1~5mol/L of the hydrochloric acid.
Preferably, the step A) in suspension concave soil a concentration of 200~300g/L.
Preferably, the mass ratio of the chitosan and the recessed soil of acidification is 1:(50~200).
Preferably, the volume of the butyl titanate and the mass ratio of the chitosan/attapulgite material are 5:(1~5).
Preferably, the deacetylation of the chitosan is 85~90%.
Preferably, the volume ratio of the absolute ethyl alcohol, nitric acid and water is (10~30):(5~20):1.
The mixed liquor volume of the absolute ethyl alcohol, nitric acid and water and the mass ratio of the chitosan/attapulgite material are (10~20):(25~35).
The present invention provides a kind of attapulgite composite material, including be acidified recessed soil and be supported on the chitosan being acidified on recessed soil and Titanium dioxide;The chitosan is (0.1~10) with the mass ratio for being acidified recessed soil:100.The present invention is by TiO2, CTS be carried on it is recessed On the carrier of this high-specific surface area of soil, TiO is effectively prevented for carrier with recessed soil2Agglomeration, and chitosan is negative It carries as TiO2Provide more attachment sites so that particle is more dispersed, uniform.Modified recessed soil structure is changed by sheet Cellular, specific surface area increase, surface amino groups and hydroxyl quantity increase, and enhance the absorption property of recessed soil.The experimental results showed that Attapulgite composite material in the present invention all has removal rate to pollutant humic acid common in water process, Congo red, Cr (VI) Stablize the effect 90%.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis The attached drawing of offer obtains other attached drawings.
Fig. 1 is the SEM figures that recessed soil is acidified in the embodiment of the present invention 2;
The SEM figures that Fig. 2 is CTS/ATP in the embodiment of the present invention 2;
Fig. 3 is TiO in the embodiment of the present invention 32The SEM figures of/CTS/ATP;
Fig. 4 is TiO in the embodiment of the present invention 22/ CTS/ATP is to the removal rate of Cr (VI) with the change curve of dosage;
Fig. 5 is TiO in the embodiment of the present invention 22/ CTS/ATP is to the removal rate of Cr (VI) with the change curve of pH value;
Fig. 6 is TiO in the embodiment of the present invention 22/ CTS/ATP is to the removal rate of Cr (VI) with the change curve of adsorption time;
Fig. 7 is TiO in the embodiment of the present invention 22/ CTS/ATP is to the removal rate of humic acid with the change curve of dosage;
Fig. 8 is TiO in the embodiment of the present invention 22/ CTS/ATP is to the removal rate versus time curve of humic acid;
Fig. 9 is TiO in the embodiment of the present invention 22/ CTS/ATP is to Congo red removal rate with the change curve of dosage;
Figure 10 is TiO in the embodiment of the present invention 22/ CTS/ATP is to Congo red removal rate with the change curve of pH value;
Figure 11 is TiO in the embodiment of the present invention 22/ CTS/ATP is bent with the variation of adsorption time to Congo red removal rate Line;
Figure 12 is influence of the different method of modifying of the present invention to recessed soil granularity.
Specific embodiment
The present invention provides a kind of attapulgite composite material, including be acidified recessed soil and be supported on the chitosan being acidified on recessed soil and Titanium dioxide;
The chitosan is 1 with the mass ratio for being acidified recessed soil:(50~200).
In the present invention, the recessed soil of the acidification is acidified to obtain by the recessed brilliant hydrochloric acid of soil, the present invention to the source of the recessed soil with Performance does not have a special limitation, and the recessed soil employed in the present invention has layer structure;The chitosan and the matter for being acidified recessed soil Amount is than being (0.1~10):100, preferably (1~8):100, more preferably (1~5):100.
Attapulgite composite material in the present invention is porous structure, and aperture is preferably preferably 100~150nm, more preferably 110~140nm, most preferably 120~130nm, specifically, can be 129nm;The grain size of the attapulgite composite material is preferably 1~5 μm, more preferably 2~4 μm, most preferably 2.52~3 μm.
The present invention also provides a kind of preparation methods of attapulgite composite material, include the following steps:
A) recessed soil with hydrochloric acid solution is mixed, suspension is centrifuged and dried, obtains being acidified recessed soil;
B) the recessed soil of the acidification is added in chitosan solution, bumps are modified, is then centrifuged and is dried, are obtained To chitosan/attapulgite material;
C) chitosan/attapulgite material is added in the ethanol solution of butyl titanate, then adds in absolute ethyl alcohol, nitre The mixed solution of acid and water is dried after forming colloidal sol, obtains attapulgite composite material.
The present invention adds in natural recessed soil in hydrochloric acid solution, is configured to suspension, constant temperature oscillation, centrifugation, washing, drying, It is ground up, sieved, obtains being acidified recessed soil.
The concentration of the hydrochloric acid solution is preferably 1~5mol/L, more preferably 2~4mol/L, most preferably 3mol/L;Institute The concentration for stating suspension concave soil is preferably 200~300g/L, more preferably 240~260g/L, most preferably 250g/L.
The temperature of the constant temperature oscillation is preferably 25 DEG C;The temperature of the drying is preferably 55~65 DEG C, most preferably 60 ℃;The time of the drying is preferably 12~15 hours;200 mesh screens are crossed after the grinding.
Then chitosan is dissolved in glacial acetic acid, in 60 DEG C of water-baths, being gathered with 30~40min of magnetic stirrer to shell Sugar is completely dissolved, and is added in and is acidified recessed soil, is stirred, is dried after centrifuge washing, is ground up, sieved, obtain chitosan/recessed soil Material (CTS/ATP).
The volume fraction of the glacial acetic acid is preferably 1~4%, and more preferably 2~3%;The deacetylation of the chitosan Preferably 85~90%;The chitosan is preferably 1 with the mass ratio for being acidified recessed soil:(50~200), more preferably 1:(100~ 150);200 mesh screens are crossed after the grinding;The temperature of the drying is preferably 55~65 DEG C, most preferably 60 DEG C;The drying Time be preferably 12~15 hours.
Sour four butyl esters of peptide are slowly dropped into absolute ethyl alcohol, add in glacial acetic acid control hydrolysis rate, stirring adds in shell and gathers Sugar/attapulgite material is slowly added dropwise absolute ethyl alcohol, nitric acid, distillation water mixed liquid, is dried after forming colloidal sol, sieving of milling obtains recessed Soil composite material (TiO2/CTS/ATP)。
The volume ratio of the butyl titanate, absolute ethyl alcohol and glacial acetic acid is preferably (1~10):(10~20):1, it is more excellent It is selected as (4~6):(14~16):1, more preferably 5:15:1;The volume of the butyl titanate and the chitosan/recessed native material The mass ratio of material is preferably 5:(1~5), more preferably 5:(2~4);The volume ratio of the absolute ethyl alcohol, nitric acid and water is preferred For (10~30):(5~20):1, more preferably (20~25):(10~15):1.The mixing of the absolute ethyl alcohol, nitric acid and water The mass ratio of liquor capacity and the chitosan/attapulgite material is (10~20):(25~35), more preferably (14~16): (29~31).The temperature of the drying is preferably 50~60 DEG C;The time of the drying is preferably 12~15 hours;The grinding 200 mesh screens are crossed afterwards.
The present invention provides a kind of attapulgite composite material, including be acidified recessed soil and be supported on the chitosan being acidified on recessed soil and Titanium dioxide;The chitosan is (0.1~10) with the mass ratio for being acidified recessed soil:100.The present invention is by TiO2, CTS be carried on it is recessed On the carrier of this high-specific surface area of soil, TiO is effectively prevented for carrier with recessed soil2Agglomeration, and chitosan is negative It carries as TiO2Provide more attachment sites so that particle is more dispersed, uniform.Modified recessed soil structure is changed by sheet Cellular, specific surface area increase, surface amino groups and hydroxyl quantity increase, and enhance the absorption property of recessed soil.The experimental results showed that Attapulgite composite material in the present invention all has removal rate to pollutant humic acid common in water process, Congo red, Cr (VI) Stablize the effect 90%.
In order to further illustrate the present invention, with reference to embodiments to a kind of attapulgite composite material provided by the invention and its Preparation method is described in detail, but cannot be understood as limiting the scope of the present invention.
Examples 1 to 3
Natural recessed soil is added in 3mol/L hydrochloric acid, is configured to the suspension containing recessed soil 250g/L, constant temperature shakes at 25 DEG C 3h is swung, 60 DEG C of drying box drying 12h are put into after centrifuge washing, milled 200 mesh screen, obtains being acidified recessed soil later.
The chitosan that 0.08g, 0.16g and 0.32g deacetylation are 90% is weighed respectively be dissolved in 100mL volume fractions be In 2% glacial acetic acid, in 60 DEG C of water-baths, it is completely dissolved with magnetic stirrer to chitosan within 30 minutes, is slowly added to 16g Recessed soil is acidified, stirs 3h, 60 DEG C of drying box drying 12h are put into after centrifuge washing, 200 mesh screens are crossed after milling, obtain chitosan Load proportioning is respectively 0.5%CTS/ATP, 1.0%CTS/ATP and 2.0%CTS/ATP.
In 60 DEG C of water-baths, measure sour four butyl esters of 10mL peptides and be slowly dropped into 30mL absolute ethyl alcohols, add in 2mL glacial acetic acid controls Hydrolysis rate processed after magnetic stirrer 15 minutes, is separately added into the CTS/ATP of the above-mentioned three kinds of proportionings of 8g, is slowly added dropwise The mixed solution of 10mL absolute ethyl alcohols, 5mL distilled water and 0.5mL nitric acid forms colloidal sol after 30 minutes, is put into 60 DEG C of drying boxes and dries Dry 12h, crosses 200 mesh screens, obtains TiO after milling2/CTS/ATP。
Fig. 1~3 are the present invention to ATP, CTS/ATP and TiO in embodiment 2 (adding in 0.16g chitosans)2/CTS/ATP The SEM figures (10000 times of amplification) of composite material, TiO is effectively prevented it can be seen from Fig. 1~3 with recessed soil for carrier2Group Poly- phenomenon, and the load of chitosan is TiO2Provide more attachment sites so that particle is more dispersed, uniform.Modified Recessed soil structure is changed into cellular, specific surface area increase by sheet, and surface amino groups and hydroxyl quantity increase, and enhance recessed soil Absorption property.
Comparative example 1
Natural recessed soil is added in 3mol/L hydrochloric acid, is configured to the suspension containing recessed soil 250g/L, constant temperature shakes at 25 DEG C 3h is swung, 60 DEG C of drying box drying 12h are put into after centrifuge washing, milled 200 mesh screen, obtains being acidified recessed soil later.
In 60 DEG C of water-baths, measure sour four butyl esters of 10mL peptides and be slowly dropped into 30mL absolute ethyl alcohols, add in 2mL glacial acetic acid controls Hydrolysis rate processed after magnetic stirrer 15 minutes, adds in 8g and is acidified recessed soil, 10mL absolute ethyl alcohols is slowly added dropwise, 5mL steams The mixed solution of distilled water and 0.5mL nitric acid forms colloidal sol after 30 minutes, is put into 60 DEG C of drying box drying 12h, 200 are crossed after milling Mesh screen obtains TiO2/ATP。
The chitosan that 0.16g deacetylations are 90% is dissolved in the glacial acetic acid that 100mL volume fractions are 2%, in 60 DEG C In water-bath, it is completely dissolved with magnetic stirrer to chitosan within 30 minutes, is slowly added to 16g TiO2/ ATP stirs 3h, from 60 DEG C of drying box drying 12h are put into after heart washing, 200 mesh screens are crossed after milling, obtain CTS/TiO2/ATP。
Difference lies in change CTS and TiO with embodiment 1 for comparative example 12Mo-Co catalyst, embodiment 1 is first to load CTS, then load TiO2, that obtain is TiO2/CTS/ATP;And comparative example 1 is first to load TiO2, then load C TS, what is obtained is CTS/TiO2/ATP.The two is as shown in table 1 to the removal effect of three kinds of pollutants (Cr (VI), Congo red, humic acid).
The modified concave-convex removal effect to water pollutant in 1 present invention of table
It tests below using the TiO in the embodiment of the present invention 22/ CTS/ATP composite materials.
The present invention is to the TiO in embodiment 22/ CTS/ATP composite materials are to Cr (VI) reaction speeds removed and acid and alkali-resistance Property test, as a result as shown in figures 4-6, wherein, Fig. 5 be a concentration of 5mg/L Cr (VI) solution, TiO2/ CTS/ATP dosages During for 0.7g/L, influence of the pH value to adsorption effect;PH=7, Cr (VI) solution of a concentration of 5mg/L, TiO are worked as in Fig. 6 expressions2/ When CTS/ATP dosages are 0.7g/L, Cr (VI) removal rate versus time curve.As shown in Figure 4, TiO2/ CTS/ATP pairs The removal effect of Cr (VI) is significantly better than ATP;As shown in Figure 5, under conditions of pH=3~10,0.7g/LTiO2/CTS/ATP More than 90% is maintained to 5mg/LCr (VI) removal rate, resistance to acid and alkali is strong, can be suitably used for acid-base value and fluctuates larger Industry Waste Water, it will be appreciated from fig. 6 that in 5min, TiO2/ CTS/ATP is swift in response with regard to that can reach preferable adsorption effect.
Fig. 7~8 are respectively the influence of adsorption time and dosage to humic acid adsorption effect, it can be seen from Fig. 7 and 8 Add 1.0g/L TiO2It is preferable with regard to that can reach in 5min in/CTS/ATP to pH=7, a concentration of 10mg/L humic acid solutions Adsorption effect is swift in response.In 1.0g/L TiO2It can reach removal rate to 10mg/L humic acid under/CTS/ATP dosages to connect Nearly 100% effect.
Fig. 9~11 are respectively the influence of dosage, pH value and the Congo red removal rate of adsorption time degree, as seen from Figure 9, In relatively low TiO2It Congo red to 100mg/L can reach removal rate under/CTS/ATP dosages (0.5g/L) close to 100% effect Fruit.It can be seen from Figure 10~11 under conditions of pH=3~8,0.5g/L TiO2/ CTS/ATP is Congo red to 100mg/L to be gone Except rate is maintained at more than 95%, and be swift in response, with regard to energy rapid-onset in 1min, reach about 70% removal rate, wherein Figure 11 PH=7, a concentration of Congo red solution of 100mg/L, TiO are worked as in expression2When/CTS/ATP dosages are 0.5g/L, Congo red removal rate Versus time curve.
Figure 12 is influence of the different method of modifying of the present invention to recessed soil granularity, and as seen from Figure 2, unmodified acidification is recessed Grogs diameter is 3.99 μm, and the grain size for only having loaded the acidification recessed native (CTS/ATP) of chitosan is 14.16 μm, has only loaded dioxy Change the recessed soil (TiO of acidification of titanium2/ ATP) grain size for 12.62 μm, and first loading chitosan carried titanium dioxide again in the application Attapulgite composite material (TiO2/ CTS/ATP) grain size be 2.52 μm.Figure 12 illustrates, TiO in the embodiment of the present invention 22/CTS/ ATP effectively prevents agglomeration so that particle is more dispersed, uniform.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of attapulgite composite material, including being acidified recessed soil and being supported on the chitosan and titanium dioxide that are acidified on recessed soil;
The chitosan is 1 with the mass ratio for being acidified recessed soil:(50~200).
2. attapulgite composite material according to claim 1, which is characterized in that the attapulgite composite material is porous structure;
The aperture of the attapulgite composite material is 100~150nm.
3. attapulgite composite material according to claim 1, which is characterized in that the grain size of the attapulgite composite material is 1~5 μm。
4. a kind of preparation method of attapulgite composite material, includes the following steps:
A) recessed soil with hydrochloric acid solution is mixed, suspension is centrifuged and dried, obtains being acidified recessed soil;
B) the recessed soil of the acidification is added in chitosan solution, bumps are modified, is then centrifuged and is dried, obtain shell Glycan/attapulgite material;
C) chitosan/attapulgite material is added in the ethanol solution of butyl titanate, then add in absolute ethyl alcohol, nitric acid and The mixed solution of water is dried after forming colloidal sol, obtains attapulgite composite material.
5. preparation method according to claim 4, which is characterized in that a concentration of 1~5mol/L of the hydrochloric acid.
6. preparation method according to claim 4, which is characterized in that the step A) in suspension concave soil concentration For 200~300g/L.
7. preparation method according to claim 4, which is characterized in that the mass ratio of the chitosan and the recessed soil of acidification It is 1:(50~200).
8. preparation method according to claim 4, which is characterized in that the volume of the butyl titanate is gathered with the shell The mass ratio of sugar/attapulgite material is 5:(1~5).
9. preparation method according to claim 4, which is characterized in that the deacetylation of the chitosan is 85~90%.
10. preparation method according to claim 4, which is characterized in that the volume ratio of the absolute ethyl alcohol, nitric acid and water is (10~30):(5~20):1;
The mass ratio of the mixed liquor volume of the absolute ethyl alcohol, nitric acid and water and the chitosan/attapulgite material for (10~ 20):(25~35).
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