CN101492165A - Organic modification method for attapulgite stone and uses of organic modified attapulgite stone - Google Patents
Organic modification method for attapulgite stone and uses of organic modified attapulgite stone Download PDFInfo
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- CN101492165A CN101492165A CNA2009101163151A CN200910116315A CN101492165A CN 101492165 A CN101492165 A CN 101492165A CN A2009101163151 A CNA2009101163151 A CN A2009101163151A CN 200910116315 A CN200910116315 A CN 200910116315A CN 101492165 A CN101492165 A CN 101492165A
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Abstract
凹凸棒石有机改性方法，其特征是以凹凸棒石粘土和葡萄糖为原料，通过水热法制备凹凸棒石/炭纳米复合材料，所述复合材料是在凹凸棒石晶体表面负载质量含量为10－20％的含有－CH官能团的无定形炭。材料表面富含－CH官能团，具有亲有机特性。与凹凸棒石原矿相比，对废水中有机污染物苯酚的脱除率可提高2－3倍以上。本发明的凹凸棒石有机改性条件温和，工艺过程简单，所得凹凸棒石含有烃类官能团，对水中有机污染物苯酚等具有较高吸附容量，可用于水中有机污染物的深度处理，或者可用于凹凸棒石的有机深加工处理。The organic modification method of attapulgite is characterized in that attapulgite clay and glucose are used as raw materials to prepare attapulgite/carbon nanocomposites by hydrothermal method, and the composite material is loaded on the surface of attapulgite crystals with a mass content of 10-20% amorphous carbon containing -CH functional groups. The surface of the material is rich in -CH functional groups and has organophilic properties. Compared with attapulgite raw ore, the removal rate of organic pollutant phenol in wastewater can be increased by more than 2-3 times. The organic modification conditions of the attapulgite of the present invention are mild, and the process is simple. The obtained attapulgite contains hydrocarbon functional groups and has a high adsorption capacity for organic pollutants in water, such as phenol, and can be used for advanced treatment of organic pollutants in water, or can be used In the organic deep processing of attapulgite.
Description
Technical field
The present invention relates to a kind of organically-modified method of attapulgite, be more particularly to the organically-modified method of attapulgite that organic pollutant removes.
Background technology
Current, it is one of urgent problem of generally facing of countries in the world that water pollutes.The quantity of wastewater effluent in China every year reaches 40,000,000,000 tons, and wherein the waste water of Organic pollutants accounts for significant proportion, and the organism that detects in the former water is kind surplus in the of 2000 nearly.Organic pollutant lifetime in water is long, scope is wide, harm is big.Its conventional treatment method mainly contains ozonation treatment, charcoal absorption, membrane separation technique, biologic treating technique, potassium permanganate oxidation method etc.But the common issue with that these methods exist is: cost height, long, system complex of cycle, even the generation by product causes secondary pollution.Advanced treatment technology and the cheap novel material of developing new former water of organic micro-pollution and waste water have become an extremely important and urgent problem.
Attapulgite is a kind of zeopan clay mineral with chain laminate structure, silica constitutes chain stratiform tetrahedral si-o film on four sides, once reversing of the free oxygen of silicon-oxy tetrahedron towards per 4 cycles generation, cause forming between unit layer the crystalline structure of one-dimensional channels formula, and present the fibrous crystals form.Attapulgite single crystal diameter is 30～50nm, has huge specific surface area, shows nano effect, adsorption activity and chemically reactive, is a kind of natural nano-mineral material of excellent performance.China's attapulgite clay reserves are abundant, and are cheap, are applied to advanced treatment of industrial waste water and have low cost and other advantages.Though attapulgite has bigger surface-area, strongly hydrophilic cause it to the avidity of organic pollutant a little less than.Therefore, need carry out attapulgite organically-modified to improve adsorptive power to organic substance.At present, what the organically-modified research of attapulgite was more is to utilize some tensio-active agents such as cetyl trimethylammonium bromide HDTMA, bromohexadecane yl pyridines CPB etc. that it is carried out modification, and some contain charcoal functional group to make the attapulgite area load.Yet the surfactant-modified shortcomings such as method is loaded down with trivial details, cost height that exist.People's high-temperature heat treatment such as Pollard, Tsai, Leboda carclazyte that gives up is found organic high temperature carbonization in the useless carclazyte, has prepared the attapulgite/carbon composite with certain functional group, and organic pollutant is had very strong selective adsorption.But thermal treatment needs 700 ℃ higher calcining temperature, needs atmosphere protection, the experimental implementation complexity, and industrial cost increases.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, provide a kind of modification route simple, raw material sources are extensive, the organically-modified method of attapulgite with low cost, the present invention provides the application of the machine modified attapulgite that obtains by this method simultaneously, by improving close organic property of attapulgite, improve it to the organic pollutant adsorption ability.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the organically-modified method of attapulgite of the present invention are to be raw material with attapulgite clay and glucose, by Hydrothermal Preparation attapulgite/carbon nanometer composite material, described matrix material is to be the amorphous carbon of the containing of 10-20%-CH functional group at attapulgite plane of crystal load quality content.
The characteristics of the organically-modified method of attapulgite of the present invention are to operate as follows:
A, selection attapulgite content are not less than 98% attapulgite clay raw ore, are crushed into the attapulgite clay powder by 200 mesh sieves;
B, be 0.25 with attapulgite clay and glucose according to attapulgite clay and glucose weight ratio: 1-4: 1 mixes, stir into uniform slurry, further carry out ultra-sonic dispersion, or high-speed stirring disperse mixing solutions, the pH value that adopts NaOH to regulate mixing solutions is 6-10;
C, described mixed solution is transferred in the hydrothermal reaction kettle, the filling ratio of hydrothermal reaction kettle volume remains on 70-80%; Temperature of reaction is 100-180 ℃, and carbonization time is 4-48 hour; After carbonization reaction finished, product was dried down at 80-100 ℃ after naturally cooling, washing, and obtains organically-modified concave and convex rod stone powder through pulverizing.
Organically-modified attapulgite clay through the method for preparing gained is that described organically-modified concave and convex rod stone powder directly is added to processed water body as the characteristics that sorbent material is used for the method for water treatment; When the concentration of phenol was 5mg/L in the described processed water body, the solid-to-liquid ratio of organically-modified concave and convex rod stone powder dosage and processed phenol solution volume was 1: 100-4: 100g/ml.
Compared with the prior art, the invention has the advantages that:
1, in the inventive method, under hydrothermal condition, attapulgite has kept original pattern and crystalline structure, and its plane of crystal has inductive effect, makes that charcoal obtains attapulgite/carbon nanometer composite material in its surface growth after the charing of glucose hydro-thermal.Compare with 500 ℃ of-1000 ℃ of high-temperature calcination methods of routine, the inventive method hydrothermal condition temperature is lower than 180 ℃, and need not atmosphere protection, need not to add any tensio-active agent, is a kind of organically-modified method of attapulgite of environmental protection.
2, the present invention is loaded with after the machine charcoal by hydrothermal method, makes close organic property of attapulgite obtain very big improvement, and rate for removing organic pollutant phenol is reached more than 80%.
Description of drawings
Figure 1A is 1: 1 for recessed soil with the glucose quality ratio, and the pH value is 9,180 ℃ of temperature of reaction, and the reaction times is the TEM photo under the 48h.
Figure 1B is 1: 2 for recessed soil with the glucose quality ratio, and the pH value is 7,160 ℃ of temperature of reaction, and the reaction times is the TEM photo under the 12h.
Fig. 1 C is that recessed soil is 1: 4 with the glucose quality ratio, and the pH value is 6.8,180 ℃ of temperature of reaction, and the reaction times is the SEM photo under the 48h.
The IR figure of Fig. 2 the inventive method modified attapulgite (condition stub of corresponding diagram 1) and attapulgite raw ore.
Below the invention will be further described by embodiment.
Specific implementation method
The preparation of organically-modified attapulgite
Embodiment 1:
Get 1g attapulgite clay and 1g glucose, mix in 100ml distilled water, ultra-sonic dispersion 30 minutes is 9 with NaOH regulator solution pH value simultaneously.Finely dispersed mixed solution is transferred in the tetrafluoroethylene water heating kettle, and filling ratio remains on 80%.180 ℃ of temperature of reaction, charing 48 hours.Reaction naturally cools to room temperature with product after finishing, and collection product centrifugation and water and ethanol obtain the black product 100 ℃ of oven dry after alternately washing.It is 14% that ultimate analysis obtains carbon content.Infrared analysis as can be known, attapulgite/carbon composite contains organo-functional groups such as C-H, as the curve a among Fig. 2, the product pattern characterizes (shown in Figure 1A) by TEM, the amorphous carbon of having found on attapulgite load.
Embodiment 2:
Get 1g attapulgite clay and 2g glucose, mix in 100ml distilled water, ultra-sonic dispersion is 7 with NaOH regulator solution pH value simultaneously.Finely dispersed mixed solution is transferred in the tetrafluoroethylene water heating kettle, and filling ratio remains on 75%.160 ℃ of temperature of reaction, charing 12 hours.Reaction naturally cools to room temperature with product after finishing, and collection product centrifugation and water and ethanol obtain the brown product 80 ℃ of oven dry after alternately washing.Infrared analysis as can be known, attapulgite/carbon composite contains organo-functional groups such as C-H, as curve b among Fig. 2.The product pattern characterizes (shown in Figure 1B) by TEM, the amorphous carbon of having found on attapulgite load.
Embodiment 3:
Get 1g attapulgite clay and 4g glucose, in 100ml distilled water, mix ultra-sonic dispersion.The solution initial pH value is 6.8, and finely dispersed mixed solution is transferred in the tetrafluoroethylene water heating kettle, and filling ratio remains on 80%.180 ℃ of temperature of reaction, charing 48 hours.Reaction naturally cools to room temperature with product after finishing, and collection product centrifugation and water and ethanol obtain the black product 90 ℃ of oven dry after alternately washing.It is 21% that ultimate analysis obtains carbon content.Infrared analysis as can be known, attapulgite/carbon composite contains organo-functional groups such as C-H, shown in curve c among Fig. 2.The product pattern characterizes shown in Fig. 1 C by SEM, found that, on attapulgite load amorphous carbon.
Curve d is the infrared spectrogram of attapulgite raw ore among Fig. 2.
Organic pollutant removes test
Prepared modified attapulgite stone powder directly is added in the phenol solution of 5mg/L 30 ℃ of following isothermal vibrations; Solid-to-liquid ratio is 1: 100-4: 100g/ml, and this solid-to-liquid ratio is meant the ratio of organically-modified attapulgite dosage and processed phenol solution volume, vibration absorption 12 hours, the phenol decreasing ratio is more than 80%.
Claims (3)
1, the organically-modified method of attapulgite, it is characterized in that with attapulgite clay and glucose be raw material, by Hydrothermal Preparation attapulgite/carbon nanometer composite material, described matrix material is to be the amorphous carbon that contains a CH functional group of 10-20% at attapulgite plane of crystal load quality content.
2, the organically-modified method of attapulgite according to claim 1 is characterized in that operating as follows:
A, selection attapulgite content are not less than 98% attapulgite clay raw ore, are crushed into the attapulgite clay powder by 200 mesh sieves;
B, be 0.25 with attapulgite clay and glucose according to attapulgite clay and glucose weight ratio: 1-4: 1 mixes, stir into uniform slurry, further carry out ultra-sonic dispersion, or high-speed stirring disperse mixing solutions, the pH value that adopts NaOH to regulate mixing solutions is 6-10;
C, described mixed solution is transferred in the hydrothermal reaction kettle, the filling ratio of hydrothermal reaction kettle volume remains on 70-80%; Temperature of reaction is 100-180 ℃, and carbonization time is 4-48 hour; After carbonization reaction finished, product was dried down at 80-100 ℃ after naturally cooling, washing, and obtains organically-modified concave and convex rod stone powder through pulverizing.
3, a kind of organically-modified attapulgite clay sorbent material for preparing through the described method of claim 1 is used for the method for water treatment, it is characterized in that described organically-modified concave and convex rod stone powder directly is added in the processed water body; When the concentration of phenol was 5mg/L in the described processed water body, the solid-to-liquid ratio of organically-modified concave and convex rod stone powder dosage and processed phenol solution volume was 1: 100-4: 100g/ml.
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| CN102188952A (en) * | 2011-05-12 | 2011-09-21 | 西北师范大学 | Multifunctional palygorskite base adsorbing material |
| CN102205972A (en) * | 2011-04-19 | 2011-10-05 | 兰州大学 | Modification method of attapulgite |
| CN102614851A (en) * | 2012-04-09 | 2012-08-01 | 西北师范大学 | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater |
| CN102974320A (en) * | 2012-12-18 | 2013-03-20 | 合肥工业大学 | Method for preparing organic modified attapulgite adsorbent |
| CN103191696A (en) * | 2013-04-10 | 2013-07-10 | 合肥工业大学 | Method for improving adsorption property of attapulgite by using hydrothermal process |
| CN104289179A (en) * | 2014-09-24 | 2015-01-21 | 合肥工业大学 | Method for preparing attapulgite/carbon composite adsorbent by one-step carbonization-activation |
| CN104445240A (en) * | 2014-12-05 | 2015-03-25 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for in-situ preparation of organized mixed-dimension nanometer material by using attapulgite |
| CN104891958A (en) * | 2015-05-20 | 2015-09-09 | 合肥工业大学 | In-situ preparation method of ceramic/carbon composite material by organic clay hot-pressing |
| CN105461974A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Modified attapulgite for rubber reinforcing, and preparation method thereof |
| CN105461975A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Natural rubber/attapulgite nanometer composite material preparation method |
| CN107805050A (en) * | 2017-09-30 | 2018-03-16 | 望江县中山新型建材有限公司 | It is a kind of that the method for being incubated high-strength sintered brick is prepared using iron tailings |
| CN108295813A (en) * | 2018-03-17 | 2018-07-20 | 宁夏大学 | Montmorillonite/carbon ball compound adsorbent and preparation method thereof and its application and detection device |
| CN110092505A (en) * | 2019-05-26 | 2019-08-06 | 北京化工大学 | A kind of method of Concave-convex clay rod processing wastewater containing phenol |
| CN111003820A (en) * | 2019-12-27 | 2020-04-14 | 东北石油大学 | A kind of solid slow-release scale inhibitor and preparation method thereof |
| CN111569640A (en) * | 2020-05-21 | 2020-08-25 | 赵兰坤 | Threonine fermentation tail gas environment-friendly treatment process |
| CN113856626A (en) * | 2021-10-11 | 2021-12-31 | 盱眙凹土能源环保材料研发中心 | Method for hydrothermal preparation of attapulgite-activated carbon composite material by attapulgite decoloration waste soil |
| CN115970635A (en) * | 2022-12-26 | 2023-04-18 | 安徽世倾环保科技有限公司 | A modified attapulgite-based adsorption material and its preparation method |
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2009
- 2009-03-09 CN CNA2009101163151A patent/CN101492165A/en active Pending
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| CN102205972A (en) * | 2011-04-19 | 2011-10-05 | 兰州大学 | Modification method of attapulgite |
| CN102205972B (en) * | 2011-04-19 | 2013-03-20 | 兰州大学 | Modification method of attapulgite |
| CN102188952A (en) * | 2011-05-12 | 2011-09-21 | 西北师范大学 | Multifunctional palygorskite base adsorbing material |
| CN102614851B (en) * | 2012-04-09 | 2013-06-12 | 西北师范大学 | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater |
| CN102614851A (en) * | 2012-04-09 | 2012-08-01 | 西北师范大学 | Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater |
| CN102974320B (en) * | 2012-12-18 | 2015-09-16 | 合肥工业大学 | A kind of preparation method of organically-modified attapulgite adsorbent |
| CN102974320A (en) * | 2012-12-18 | 2013-03-20 | 合肥工业大学 | Method for preparing organic modified attapulgite adsorbent |
| CN103191696A (en) * | 2013-04-10 | 2013-07-10 | 合肥工业大学 | Method for improving adsorption property of attapulgite by using hydrothermal process |
| CN105461975B (en) * | 2014-08-08 | 2019-01-18 | 兰州大学 | A kind of preparation method of natural rubber/palygorskite nano composite material |
| CN105461974A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Modified attapulgite for rubber reinforcing, and preparation method thereof |
| CN105461975A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Natural rubber/attapulgite nanometer composite material preparation method |
| CN105461974B (en) * | 2014-08-08 | 2019-01-18 | 兰州大学 | A kind of preparation method of modified attapulgite used for rubber reinforcement |
| CN104289179A (en) * | 2014-09-24 | 2015-01-21 | 合肥工业大学 | Method for preparing attapulgite/carbon composite adsorbent by one-step carbonization-activation |
| CN104445240A (en) * | 2014-12-05 | 2015-03-25 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for in-situ preparation of organized mixed-dimension nanometer material by using attapulgite |
| CN104891958A (en) * | 2015-05-20 | 2015-09-09 | 合肥工业大学 | In-situ preparation method of ceramic/carbon composite material by organic clay hot-pressing |
| CN107805050A (en) * | 2017-09-30 | 2018-03-16 | 望江县中山新型建材有限公司 | It is a kind of that the method for being incubated high-strength sintered brick is prepared using iron tailings |
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| CN111003820A (en) * | 2019-12-27 | 2020-04-14 | 东北石油大学 | A kind of solid slow-release scale inhibitor and preparation method thereof |
| CN111569640A (en) * | 2020-05-21 | 2020-08-25 | 赵兰坤 | Threonine fermentation tail gas environment-friendly treatment process |
| CN113856626A (en) * | 2021-10-11 | 2021-12-31 | 盱眙凹土能源环保材料研发中心 | Method for hydrothermal preparation of attapulgite-activated carbon composite material by attapulgite decoloration waste soil |
| CN115970635A (en) * | 2022-12-26 | 2023-04-18 | 安徽世倾环保科技有限公司 | A modified attapulgite-based adsorption material and its preparation method |
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