CN107694523A - A kind of kaolin composite material and preparation method thereof - Google Patents
A kind of kaolin composite material and preparation method thereof Download PDFInfo
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- CN107694523A CN107694523A CN201710986183.2A CN201710986183A CN107694523A CN 107694523 A CN107694523 A CN 107694523A CN 201710986183 A CN201710986183 A CN 201710986183A CN 107694523 A CN107694523 A CN 107694523A
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- kaolin
- composite material
- intercalation modifying
- intercalation
- titania
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention provides a kind of kaolin composite material, and it includes intercalation modifying kaolin and the titania nanoparticles being supported on the intercalation modifying kaolin, and the intercalation modifying kaolin is cetyl trimethylammonium bromide intercalation modifying kaolin.The present invention also provides a kind of preparation method of above-mentioned kaolin composite material.Above-mentioned kaolin composite material provided by the invention can be for handling the PPCPs pollutants such as the chloramphenicol in waste water, penicillin, erythromycin, streptomysin, vancomycin, pipemidic acid, C14H10Cl2NNaO2, and treatment effect is relatively good.
Description
Technical field
The present invention relates to a kind of water treatment agent and preparation method thereof, more particularly to a kind of it is used to adsorb PPCPs pollutants
Kaolin composite material and preparation method thereof.
Background technology
PPCPs is medicine and the abbreviation of personal protective articles, is widely used in the mankind, domestic animals, among fish.Composition
PCCPs chemical composition about more than 3000 kind mainly include two major classes：One kind is medicine, including antibiotic, analgestic, is swashed
Element, diuretics, anodyne, steroids, caffeine etc.；Another kind of is personal protective articles, including spices, hair jelly, cosmetics etc..Mesh
The preceding different types of PPCPs remained in global environment mainly by antibiotic and pyrolysis analgesic drug headed by, due to big portion
Divide PPCPs volatility relatively low or not degradable, thus major part is remained in water environment, detected level is also larger, PPCPs is
The health and ecological environment of the mankind are threatened.China is production of active pharmaceutical substances state maximum in the world, while is in the world
The country of consumption of 3 active medicines before ranking.According to statistics, China has reclaimed 0.69 × 10 between 20078m3Waste water recharge to underground
It is especially more common in the northern this phenomenon of shortage of water resources in water, however, but detecting largely to plant in these recycle-waters
The PPCPs of class.
PCCPs treatment technology mainly includes transfer method, absorption method and edman degradation Edman etc. at present.Wherein, transfer method is mainly
Refer to migration, filtering and the solidification of natural environment and natural soil to PPCPs.But there is the migration through natural environment in transfer method
It is limited with filter effect, and soil curing efficiency it is often relatively low the problems such as.Edman degradation Edman is primarily referred to as advanced oxidation processes (H2O2/
UV), using the stronger material of certain oxidation activity, and high energy radiation or excite lower step by step decomposition of the realization to PPCPs very
It is extremely degradable.It is significant using cycle development of the advanced oxidation processes degraded PPCPs to ecological environment, however, at present
Research process it is complicated, there is high energy consumption, high cost relative to traditional solid phase adsorption method, and relatively difficult to achieve right
PPCPs's is degradable, limits the application of this method.
Absorption method is primarily referred to as using natural clay mineral and some artificial synthesized feature sorbing materials to PPCPs
Adsorbed and solidification, can also be carried out on the stronger clay mineral of some absorption properties it is function modified, to realize height
Imitate the effect of solidification.Relative to transfer method, solid phase adsorption method is had because using special adsorption structure and feature adsorption group
There is the advantage efficiently solidified.In addition, advanced oxidation degradation technical research is immature, cost is high, application is poor, and solidification is real
Existing degradable important prerequisite, solid phase adsorption method are still PPCPs pollution treatment methods the most frequently used at present.But all kinds of viscous
In native mineral, kaolin is bad to PPCPs water treatment effects, has much room for improvement.
The content of the invention
In view of this, it is necessory to provide a kind of kaolin composite material and preparation method thereof, to improve kaolin pair
The treatment effect of PPCPs waste water.
The present invention provides a kind of kaolin composite material, and it includes intercalation modifying kaolin and is supported on intercalation modifying height
Titania nanoparticles (TiO on the soil of ridge2), and the intercalation modifying kaolin is cetyl trimethylammonium bromide
(CTAB) intercalation modifying kaolin.
Based on above-mentioned, the quality of cetyl trimethylammonium bromide and kaolin original soil in the intercalation modifying kaolin
Than for 0.5~1:10.
Based on above-mentioned, the titania nanoparticles are 1 with the kaolinic mass ratio of the intercalation modifying：(14~
30), the particle diameter of the titania nanoparticles is 10~100nm.
Based on above-mentioned, the titania nanoparticles are supported on the kaolinic surface of the intercalation modifying.
Based on above-mentioned, the titania nanoparticles are supported in the kaolinic intercalation configuration of the intercalation modifying.
The present invention also provides a kind of preparation method of above-mentioned kaolin composite material, and it comprises the following steps：
Intercalation modifying kaolin is prepared first to add kaolin original soil in deionized water and is uniformly mixed, and is then heated to
60~80 DEG C, 0.5~1h of constant temperature, obtain suspension；Cetyl trimethylammonium bromide is added into the suspension, normal temperature stirs
24~48h is mixed, obtains the blended liquid that concentration is 10.5%~11% (w/v)；
Prepared by presoma prepares titania gel solution using sol-gel process, by the titania gel solution
1~4h, filtering are mixed with the blended liquid, and 4~6h is dried at 85~100 DEG C, obtains precursor particle material；
Product prepares and the precursor particle material is placed in Muffle furnace, and the Muffle furnace is with constant heating rate liter
Temperature is to 550~620 DEG C, and calcining at constant temperature can obtain the kaolin composite material.
Based on above-mentioned, in the step of prepared by the presoma, the titania gel solution be using butyl titanate as
Titanium source, and mixed with absolute ethyl alcohol, anhydrous acetic acid and 95% ethanol solution, prepared using sol-gel process, and described two
The concentration of titanium oxide gel solution is 20~30g/L.
Based on above-mentioned, in the step of prepared by the product, the heating rate of the Muffle furnace for 2 DEG C/min~4 DEG C/
Min, the time of the calcining at constant temperature is 8~12h.
Compared with prior art, in kaolin composite material provided by the invention, the intercalation modifying kaolin is tool
There is the loose structure of large specific surface area, and kaolin can improve its interlamellar spacing by intercalation modifying, so the intercalation
Modified kaolin can adsorb PPCPs, and by PPCPs solidifications wherein；Meanwhile the titania nanoparticles can load
Into the kaolinic surface of the intercalation modifying and/or kaolinic intercalation configuration, because the titania nanoparticles have
There is photocatalysis, the PPCPs of macromolecular can be decomposed into the material of small molecule by it, the material of the small molecule not only easy quilt
It to kaolinic surface, can also be adsorbed in kaolinic intercalation, further increase energy of adsorption of the kaolin to PPCPs
Power, so as to improve treatment effect of the kaolin to PPCPs waste water.In addition, titania nanoparticles are carried on the intercalation
In the surface of modified kaolin and/or kaolinic intercalation, the face body ratio of catalyst is substantially increased, while avoids titanium dioxide
The loss of titanium nano particle, extend catalyst service life, reduce processing cost, and repeatable utilization.Therefore, the present invention provides
Adsorbent can be used for handling chloramphenicol, penicillin, erythromycin, streptomysin, vancomycin, pipemidic acid, double chlorine in waste water
The PPCPs pollutants such as fragrant sour sodium, and treatment effect is relatively good.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
The present embodiment provides a kind of kaolin composite material, and it includes CTAB intercalation modifyings kaolin and is supported on the CTAB
Titania nanoparticles (TiO on intercalation modifying kaolin2).Specifically, the particle diameter of the titania nanoparticles is
10~50nm, the TiO2Nano particle is supported in the kaolinic surface of the CTAB intercalation modifyings or intercalation configuration, and institute
State TiO2Nano particle and the kaolinic mass ratio of CTAB intercalation modifyings are about 1：14.
The present embodiment also provides a kind of preparation method of above-mentioned kaolin composite material, and it comprises the following steps：
It is prepared by intercalation modifying kaolin：First the kaolin original soil of 10 mass parts is added in the deionized water of 100 volume powder
It is uniformly mixed, is then heated to 70 DEG C, constant temperature 1h, obtains suspension；The 16 of 1 mass parts are added into the suspension
Alkyl trimethyl ammonium bromide, stirring at normal temperature 36h, obtain the blended liquid that concentration is 11% (w/v)；
It is prepared by presoma：Take 34mL butyl titanate to be added in the separatory funnel for the absolute ethyl alcohol for filling 80mL to mix
To solution A, separately take 20mL glacial acetic acid and 85mL 95% ethanol to be uniformly mixed so as to obtain solution B, solution A is slowly added drop-wise to B solution
In and promptly stirred with magnetic stirring apparatus to obtain transparent TiO2Gel solution；According to certain ratio, by the TiO2Gel
Solution and the blended liquid that the concentration is 11% (w/v) mix 2h, filtering, and 6h is dried at 100 DEG C, obtain presoma
Particulate material；
It is prepared by product：The precursor particle material is placed in Muffle furnace, the Muffle furnace is with 2 DEG C/min heating speed
Rate is warming up to 600 DEG C, and calcining at constant temperature 10h can obtain the kaolin composite material.
Embodiment 2
The present embodiment provides a kind of kaolin composite material, structure and the offer of embodiment 1 of the kaolin composite material
The structure of PPCPs pollutants is essentially identical, is in place of main difference：The TiO2Nano particle and the CTAB intercalation modifyings
Kaolinic mass ratio is about 1：20.
The preparation method for the above-mentioned kaolin composite material that the embodiment provides and the preparation method that embodiment 1 provides are basic
It is identical, it is in place of main difference：The present embodiment is in the step of prepared by the product, and Muffle furnace is with 3 DEG C/min heating speed
Rate is warming up to 620 DEG C, and the calcining at constant temperature time is 12h.
Embodiment 3
The present embodiment provides a kind of kaolin composite material, structure and the offer of embodiment 1 of the kaolin composite material
The structure of PPCPs pollutants is essentially identical, is in place of main difference：The TiO2The particle diameter of nano particle is 30~80nm,
The TiO2Nano particle is substantially supported on the surface of the CTAB intercalation kaolins soil, and the TiO2Nano particle with it is described
The kaolinic mass ratio of CTAB intercalation modifyings is about 1：30.
The preparation method for the above-mentioned kaolin composite material that the embodiment provides and the preparation method that embodiment 1 provides are basic
It is identical, it is in place of main difference：The present embodiment is in the step of prepared by the product, and Muffle furnace is with 4 DEG C/min heating speed
Rate is warming up to 580 DEG C, and the calcining at constant temperature time is 8h.
Embodiment 4
The present embodiment provides a kind of kaolin composite material, structure and the offer of embodiment 3 of the kaolin composite material
The structure of PPCPs pollutants is essentially identical, is in place of main difference：The TiO2Nano particle and the CTAB intercalation modifyings
Kaolinic mass ratio is about 1：25.
The preparation method for the above-mentioned kaolin composite material that the embodiment provides and the preparation method that embodiment 3 provides are basic
It is identical, it is in place of main difference：In the present embodiment, 0.5 parts by weight are used in the step of prepared by the intercalation modifying kaolin
CTAB；In the step of prepared by the product, Muffle furnace is warming up to 610 DEG C with 3 DEG C/min heating rate, during calcining at constant temperature
Between be 10h.
Performance test
1st, filled respectively in the cylindrical reactor that three specifications are identical, effective volume is 10L equivalent kaolin original soil,
(mass ratio of CTAB and kaolin original soil is 1 to CTAB intercalation modifyings kaolin:10) the above-mentioned kaolin provided with embodiment 1 is answered
These three adsorbents of condensation material, to chloramphenicol simulated wastewater (COD under the conditions of same operational factor：150~200mg/L) carry out
Advanced treating, treatment effect are shown in Table 1, wherein, process conditions：Wastewater pH is 7~8, HRT 30min.
The water treatment efficiency table of 1 different adsorbents of table
As shown in Table 1, under identical service condition, water of the kaolin composite material provided by the invention to PPCPs waste water
Treatment effect is far above kaolin original soil, compound compared to CTAB intercalation modifying kaolin, kaolin provided in an embodiment of the present invention
Material is improved more than 15% to the COD clearances of PPCPs waste water.
2nd, the present invention for filling equivalent respectively in the cylindrical reactor that four specifications are identical, effective volume is 10L is implemented
The above-mentioned kaolin composite material that example 1 provides, several different PPCPs simulated wastewaters are carried out under the conditions of identical operational factor deep
Degree processing, process conditions：Waste water HRT is 30min, and treatment effect is shown in Table 2.
The different PPCPs wastewater biochemicals ponds of table 2 go out water treatment efficiency table
As shown in Table 2：At certain operational conditions, kaolin composite material provided in an embodiment of the present invention is to difference
The COD clearances of PPCPs waste water have 55%~75%, and kaolin composite material provided in an embodiment of the present invention is to PPCPs
The process performance of waste water has spectrum.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
The embodiment of the present invention can be modified or equivalent substitution is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical scheme, it all should cover among the claimed technical scheme scope of the present invention.
Claims (8)
- A kind of 1. kaolin composite material, it is characterised in that：It includes intercalation modifying kaolin and is supported on intercalation modifying height Titania nanoparticles on the soil of ridge, and the intercalation modifying kaolin is that cetyl trimethylammonium bromide intercalation modifying is high Ridge soil.
- 2. kaolin composite material according to claim 1, it is characterised in that：16 in the intercalation modifying kaolin The mass ratio of alkyl trimethyl ammonium bromide and kaolin original soil is 0.5~1: 10.
- 3. kaolin composite material according to claim 1 or 2, it is characterised in that：The titania nanoparticles with The kaolinic mass ratio of intercalation modifying is 1：（14~30）, the particle diameter of the titania nanoparticles is 10~100 nm。
- 4. kaolin composite material according to claim 3, it is characterised in that：The titania nanoparticles are supported on The kaolinic surface of intercalation modifying.
- 5. kaolin composite material according to claim 4, it is characterised in that：The titania nanoparticles are supported on In the kaolinic intercalation configuration of intercalation modifying.
- 6. a kind of preparation method of the kaolin composite material described in claim 1, it comprises the following steps：Intercalation modifying kaolin is prepared first to add kaolin original soil in deionized water and is uniformly mixed, and is then heated to 60 ~80 DEG C, the h of constant temperature 0.5~1, obtain suspension；Cetyl trimethylammonium bromide is added into the suspension, normal temperature stirs 24~48 h are mixed, obtain concentration as 10.5%~11%（w/v）Blended liquid；Presoma prepares and using sol-gel process prepares titania gel solution, by the titania gel solution with The blended liquid mixes 1~4 h, filtering, and 4~6 h are dried at 85~100 DEG C, obtains precursor particle material；Product is prepared and the precursor particle material is placed in Muffle furnace, and the Muffle furnace is heated up with constant heating rate To 550~620 DEG C, and calcining at constant temperature is that can obtain the kaolin composite material described in claim 1.
- 7. the preparation method of kaolin composite material according to claim 6, it is characterised in that：Prepared in the presoma The step of in, the titania gel solution be using butyl titanate as titanium source, and with absolute ethyl alcohol, anhydrous acetic acid and 95% second Alcoholic solution mixes, and is prepared using sol-gel process, and the concentration of the titania gel solution is 20~30 g/L.
- 8. the preparation method of the kaolin composite material according to claim 6 or 7, it is characterised in that in the product system In standby step, the heating rate of the Muffle furnace is 2 DEG C/min~4 DEG C/min, and the time of the calcining at constant temperature is 8~12 h。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793784A (en) * | 2018-07-07 | 2018-11-13 | 河源市极致知管信息科技有限公司 | One kind containing kaolin composite material and preparation method thereof |
| CN109021660A (en) * | 2018-08-20 | 2018-12-18 | 江苏中科纳特环境科技有限公司 | A kind of nano-TiO2The preparation method of kaolin intercalation material |
| CN114159559A (en) * | 2021-11-17 | 2022-03-11 | 中国地质大学（武汉） | Kaolinite composite diagnosis and treatment agent and preparation method and application thereof |
| CN114316644A (en) * | 2022-01-06 | 2022-04-12 | 深装总建设集团股份有限公司 | Environment-friendly inorganic coating for purifying indoor air and preparation method thereof |
| CN114951254A (en) * | 2022-05-11 | 2022-08-30 | 福建工程学院 | Method for preventing and controlling co-migration of micro-plastic-drug-resistant gene in soil |
| CN115926710A (en) * | 2022-11-25 | 2023-04-07 | 广州市高士实业有限公司 | Preparation of brightening glue |
| CN116102057A (en) * | 2022-11-18 | 2023-05-12 | 山西工学院 | Titanium dioxide coated kaolin as well as preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793784A (en) * | 2018-07-07 | 2018-11-13 | 河源市极致知管信息科技有限公司 | One kind containing kaolin composite material and preparation method thereof |
| CN109021660A (en) * | 2018-08-20 | 2018-12-18 | 江苏中科纳特环境科技有限公司 | A kind of nano-TiO2The preparation method of kaolin intercalation material |
| CN114159559A (en) * | 2021-11-17 | 2022-03-11 | 中国地质大学（武汉） | Kaolinite composite diagnosis and treatment agent and preparation method and application thereof |
| CN114159559B (en) * | 2021-11-17 | 2022-11-25 | 中国地质大学（武汉） | Kaolinite composite diagnosis and treatment agent and preparation method and application thereof |
| CN114316644A (en) * | 2022-01-06 | 2022-04-12 | 深装总建设集团股份有限公司 | Environment-friendly inorganic coating for purifying indoor air and preparation method thereof |
| CN114951254A (en) * | 2022-05-11 | 2022-08-30 | 福建工程学院 | Method for preventing and controlling co-migration of micro-plastic-drug-resistant gene in soil |
| CN114951254B (en) * | 2022-05-11 | 2023-11-14 | 福建工程学院 | Method for preventing and controlling microplastic-drug-resistant gene co-migration in soil |
| CN116102057A (en) * | 2022-11-18 | 2023-05-12 | 山西工学院 | Titanium dioxide coated kaolin as well as preparation method and application thereof |
| CN116102057B (en) * | 2022-11-18 | 2024-11-01 | 山西科技学院 | Titanium dioxide coated kaolin as well as preparation method and application thereof |
| CN115926710A (en) * | 2022-11-25 | 2023-04-07 | 广州市高士实业有限公司 | Preparation of brightening glue |
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Application publication date: 20180216 |