CN105126757A - Preparation method for diatomaceous earth-supported nanometer carbon composite adsorption material - Google Patents
Preparation method for diatomaceous earth-supported nanometer carbon composite adsorption material Download PDFInfo
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- CN105126757A CN105126757A CN201510574057.7A CN201510574057A CN105126757A CN 105126757 A CN105126757 A CN 105126757A CN 201510574057 A CN201510574057 A CN 201510574057A CN 105126757 A CN105126757 A CN 105126757A
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Abstract
The invention relates to a preparation method for a diatomaceous earth-supported nanometer carbon composite adsorption material, and belongs to the field of nonmetallic mineral material deep-processing and environmental engineering. The surface and pore passages of diatomaceous earth are taken as micro-reaction areas, glucose or starch is taken as a carbon source, and generated nanometer carbon particles are uniformly supported to the surface and the pore passages of diatomaceous earth to obtain the efficient nanometer carbon composite adsorption material with diatomaceous earth as a supporter by a hydrothermal synthesis method. According to the method, a process is simple, the nanometer carbon particles are uniformly and densely distributed on the surface and in the pore passages of diatomaceous earth, the adsorption of nanometer carbon and diatomaceous earth to pollutants in water is greatly improved, and nanometer carbon and diatomaceous earth have high potential application value in the field of wastewater treatment.
Description
Technical field:
The present invention relates to
a kind of preparation method of tripolite loading nano carbon composite adsorbing material, belong to nonmetallic mineral material deep processing and field of environment engineering.
Background technology:
Carbon back sorbing material is because of the absorption property of its large specific area, flourishing pore structure and excellence, and can be widely used in water treatment and air pollution treatment field, be a kind of desirable environment pollution treatment material.Active carbon adsorption material can remove most of organic matter in organic wastewater, the organic removal rate dissolved can reach more than 90% usually, BOD BOD, chemical oxygen demand COD generally can remove 30% ~ 60%, can also effectively remove some heavy metal ion in addition.But because the price comparison of merchandise active carbon is high, service life is short, the defect such as difficult for regeneration and operating cost is high, there is no method industrially uses on a large scale; Meanwhile, because nano-carbon material particle is little, surface energy is high, be easy to reunite, cause separation difficulty and its absorption property is declined.For the problems referred to above, researcher proposes the immobilization technology of nano carbon particle, loads to some natural minerals carrier surface by nano carbon particle, is prepared into loaded nano carbon granule composite adsorbing material.Four sections of documents below: the research of (1) hydro-thermal method modified attapulgite and absorption property thereof. application chemical industry, 2010,39 (4): 487-490, (2) Synthesisofanattapulgiteclaycarbonnanocompositeadsorbentbyahydrothermalcarbonization processandtheirapplicationintheremovaloftoxicmetalionsfr omwater, Langmuir, 27 (2011) 8998-9004. (3) Simultaneoussorptionof4-nitrophenoland2-nitrophenolonahy bridgeocompositebasedonsurfactant-modifiedpillared-claya ndactivatedcarbon, ChemicalEngineeringJournal, 279 (2015) 964-972. (4) Synthesisofclay/carbonadsorbentthroughhydrothermalcarbon izationofcelluloseonpalygorskite, AppliedClayScience, 95 (2014) 60-66. adopt the mode of hydro-thermal compound respectively, prepare attapulgite, montmorillonite-loaded nano-sized carbon sorbing material.Although lower as carrier material production cost using natural attapulgite, montmorillonite, palygorskite etc., but because carrier aperture is little, after loaded with nano carbon, carrier duct is mostly blocked, cause that the rate of filtration is slow, absorption property is poor, affect composite efficient adsorption effect and play and apply with actual.
Diatomite is a kind of biogenic silicastone, and main chemical compositions is noncrystalline SiO
2; Have loose, light weight, porous and duct is the characteristics such as regular distribution, stable chemical nature, specific area and pore volume are comparatively large, and absorption, fixed performance are good, are a kind of excellent adsorption carrier materials.Diatomaceous high-specific surface area, large pore volume can improve the dispersion stabilization of nano-sized carbon, the pollutant rate of adsorption and adsorption capacity; In addition, China has abundant diatomite resource, wide material sources, and production cost is lower.Document (Anewcarbon – diatomiteearthcompositeadsorbentforremovalofheavymetalsf romaqueoussolutionsandanovelapplicationidea, MicroporousandMesoporousMaterial, (217) 2015:63-70) report the preparation method of a kind of carbon and diatomaceous composite adsorbing material, the method take cellulose as carbon source, is realized the compound of diatomite and carbon by the mode of the chemical carbonizations such as 95% concentrated sulfuric acid, 65% red fuming nitric acid (RFNA) or 30% hydrogen peroxide.In the preparation process of this preparation method, the concentrated sulfuric acid used, red fuming nitric acid (RFNA), hydrogen peroxide are severe corrosive raw material, and require higher to consersion unit and production safety, and there is certain potential safety hazard, factory effluent is difficult to process and contaminated environment.
The object of this invention is the deficiency for current loaded nano carbon composite adsorbing material, and providing a kind of take diatomite as the preparation method of the diatomite/Nano Carbon efficient adsorption material of immobilization carrier.Not only the rate of adsorption is higher for this composite adsorbing material, adsorption capacity is comparatively strong, good separating effect, and production technology is simple, cost is lower, practicality good, and production process is environmentally friendly.Therefore, this kind of composite adsorbing material has a good application prospect in water treatment field.
Summary of the invention:
The present invention for carbon source, adopts hydrothermal synthesis method that the nano carbon particle of generation is loaded to diatom surface equably with glucose or starch, thus to prepare a kind of take diatomite as the Nano Carbon efficient adsorption material of carrier.
The tripolite loading nano carbon adsorbing material prepared with the present invention, diatom surface and uniform load nano carbon particle in duct in diatomite, nano carbon particle average grain diameter is 20 ~ 30nm; Nano-sized carbon load capacity is 20% ~ 50% of diatomite quality.
Its preparation method and processing step as follows:
(1) by diatomite: carbon source: the mass ratio of water=1:1 ~ 2:50 ~ 100, by diatomite, carbon source and water mixing also ultrasonic disperse 20min, obtains homodisperse suspension; Described diatomite is the diatomite that diatom content is greater than 80%, and diatom particle is as far as possible complete; Described carbon source is glucose or starch.
(2) added in autoclave by the suspension obtained in step (1) and carry out hydro-thermal reaction, wherein the volumetric filling ratio of reactor is 40 ~ 80%, at 150 ~ 300 DEG C of Water Under thermal response 6 ~ 24h;
(3) the hydro-thermal reaction product in step (2) is filtered, simultaneously with absolute ethyl alcohol and distilled water alternately washing, until cleaning solution is clear, then dries at 105 DEG C, namely obtain nano-sized carbon/composite diatomite sorbing material.
The present invention utilizes the pore structure of diatomite prosperity and stronger adsorption capacity to compensate for the defect that single nano-carbon material is easily reunited, adsorption capacity is poor; Achieve nanometer carbon nanobeads to distribute on diatomite surface and the even, fine and close of duct, substantially increase nano-sized carbon to the adsorption efficiency of pollutant and adsorption capacity, and reduce the application cost of adsorbent, and environmentally friendly after use procedure and use; And preparation technology is simple, cost is low, and practicality is good.
Accompanying drawing explanation
accompanying drawing 1for technological process of the present invention
figure;
accompanying drawing 2for the diatomaceous SEM of used carrier in the present invention
figure;
accompanying drawing 3for the SEM of tripolite loading nano carbon composite adsorbing material in the present invention
figure;
accompanying drawing 4for the TEM of tripolite loading nano carbon composite adsorbing material in the present invention
figure.
Detailed description of the invention
Below in conjunction with embodiment and
accompanying drawingproduct of the present invention is further described.
Embodiment 1:
Concrete implementation step is as follows:
Raw material is introduced: diatomite is from six Dao Gou mining areas near a river, Jilin Province, and its main chemical compositions and content are SiO
288.19%, Al
2o
33.59%, Fe
2o
31.53%, TiO
20.11%, CaO0.62%, K
2o0.55%, Na
2o0.11%.Take glucose as carbon source, glucose is pure for analyzing, and white powder, chemical formula is C
6h
12o
6h
2o.
Step of preparation process is as follows:
(1) diatomite sample ore and the 3.5g glucose of getting 2.5g are respectively placed in 75ml water, ultrasonic disperse 30min, make diatomite and glucose full and uniform dispersion in suspension.
(2) suspension that step (1) obtains is added in the hydro-thermal autoclave of 100mL, after good seal at the temperature of 180 DEG C hydro-thermal reaction 12h.Get precipitated product absolute ethyl alcohol and the distilled water alternately washing of gained, until cleaning solution is clear, then dry at 105 DEG C, and finally obtain described tripolite loading nano carbon composite adsorbing material.
The tripolite loading nano carbon composite adsorbing material of embodiment 1 diatomite material used and preparation is shown in respectively
accompanying drawing 2, 3; By
fig. 2known, diatom based on disk algae, diatom smooth surface, duct is clear; By
fig. 3, 4 known, in the tripolite loading nano carbon composite adsorbing material of gained, nano carbon particle is evenly distributed in diatom surface, and nano carbon particle average grain diameter is 20 ~ 30nm.
Embodiment 2:
Identical with step with the raw material in embodiment 1, difference is: 3.0g diatomite quality and 3.5g glucose are placed in 75ml water; Hydro-thermal reaction 14h at 200 DEG C.
Embodiment 3:
Identical with step with the raw material in embodiment 1, difference is: 2.5g diatomite quality and 3.75g glucose are placed in 75ml water; Hydro-thermal reaction 8h at 220 DEG C.
Embodiment 4:
Identical with step with the raw material in embodiment 1, difference is: 2.5g diatomite quality and 4.375g glucose are placed in 75ml water; Hydro-thermal reaction 14h at 220 DEG C.
According to method described below, the performances and parameters of final products in Measurement and Computation embodiment 1 to 4, the results are shown in of gained
table 1in.
The test of composite absorption property: in the adsorption applications of heavy metal ion and organic dye waste water, potassium bichromate and rhodamine B solution, usually used as adsorbing object, are used for testing the absorption property of sample.The adsorption rate of sample to pollutant solution is larger under given conditions, illustrates that its absorption property is better.In this detailed description of the invention, the concentration of potassium bichromate used, rhodamine B solution is 50mg/L.
Measure containing Cr (VI) waste water absorption property: the pH value regulating potassium bichromate solution is about 2.0, utilizes Stirring instrument to carry out adsorption reaction.Adopt Cr (VI) residual concentration in diphenyl carbazide spectrophotometry mensuration centrifuged supernatant, get 40ml potassium bichromate solution and the mixing of 0.25g composite sample at every turn, on reactor after hybrid reaction 12h, adopt the water system membrane filtration of 0.45um, get supernatant 550nm wavelength place on spectrophotometer and survey absorbance, then the adsorption rate computing formula of potassium bichromate solution is: adsorption rate=(C
0-C
12)/C
0× 100%, C in formula
0for the absorbance of initial potassium bichromate solution, C
12for the absorbance of potassium bichromate solution during reaction 12h.
Rhdamine B waste water absorption property measures: get 100ml rhodamine B solution and 0.1g at every turn and prepare sample mixing centrifuge tube and sample, high speed centrifugation after hybrid reaction 12h on reactor, get supernatant 554nm wavelength place on spectrophotometer and survey absorbance, then the adsorption rate computing formula of rhodamine B solution is: adsorption rate=(C
0'-C
12')/C
0' × 100%, C in formula
0' be the absorbance of initial rhodamine B solution, C
12' be the absorbance of rhodamine B solution during reaction 12h.
table 1the performance of final products and parameter in embodiment 1 to 4
Finally it should be noted that, although above in conjunction with the embodiments to invention has been detailed description; person of ordinary skill in the field can understand; under the prerequisite not departing from present inventive concept, in claims, can also change above-described embodiment and change etc.
Claims (3)
1. a preparation method for nano-sized carbon/composite diatomite sorbing material, adopts hydrothermal synthesis method that the nano carbon particle of generation is loaded to diatomite surface equably, comprises following process steps:
(1) by diatomite: carbon source: the mass ratio of water=1:1 ~ 2:50 ~ 100, by diatomite, carbon source and water mixing also ultrasonic disperse 20min, obtains homodisperse suspension;
(2) added in autoclave by the suspension obtained in step (1) and carry out hydro-thermal reaction, wherein the volumetric filling ratio of reactor is 40 ~ 80%, at 150 ~ 300 DEG C of Water Under thermal response 6 ~ 24h;
(3) the hydro-thermal reaction product in step (2) is filtered, simultaneously with absolute ethyl alcohol and distilled water alternately washing, until cleaning solution is clear, then dries at 105 DEG C, namely obtain nano-sized carbon/composite diatomite sorbing material.
2. the preparation method of a kind of nano-sized carbon/composite diatomite sorbing material according to claim 1, is characterized in that, described diatomite is the diatomite that diatom content is greater than 80%, and diatom particle is complete.
3. the preparation method of a kind of nano-sized carbon/composite diatomite sorbing material according to claim 1, is characterized in that, described carbon source is glucose or starch.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311147A (en) * | 2016-10-17 | 2017-01-11 | 中国矿业大学(北京) | Illite loaded nanocarbon compound adsorbing material and preparation method thereof |
| CN106946357A (en) * | 2017-05-08 | 2017-07-14 | 宁波市川宁环保科技有限公司 | A kind of preparation method for the filler special for artificial wetland fixed for microorganism |
| CN107042085A (en) * | 2016-10-17 | 2017-08-15 | 中国矿业大学(北京) | A kind of oxygen-enriched functional group's carbon/illite composite adsorbent material and preparation method thereof |
| CN109652022A (en) * | 2018-12-28 | 2019-04-19 | 青海大学 | A kind of preparation method of NEW TYPE OF COMPOSITE diatomite phase-changing energy storage material carrier |
| CN110270309A (en) * | 2019-07-25 | 2019-09-24 | 西南石油大学 | A kind of shale gas fracturing outlet liquid water treatment absorbent preparation method and application |
| CN110354582A (en) * | 2019-06-27 | 2019-10-22 | 重庆中轻装备有限公司 | A kind of soy sauce filtration process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031415A (en) * | 1999-07-19 | 2001-02-06 | Kagawaken Sangyo Gijutsu Shinko Zaidan | Porous molded article based on calcium silicate or silica |
| CN102600801A (en) * | 2012-04-09 | 2012-07-25 | 西北师范大学 | Preparation of waste potato residue/palygorskite composite adsorbent and application of adsorbent in treatment of potato starch processing wastewater |
| CN103055806A (en) * | 2011-10-18 | 2013-04-24 | 中国科学技术大学 | Carbon-coated attapulgite clay composite material and its preparation method |
| CN103157438A (en) * | 2013-04-10 | 2013-06-19 | 哈尔滨工业大学 | Preparation method of carbon microsphere/nanometer iron oxide magnetic composite material |
| CN103623779A (en) * | 2013-12-06 | 2014-03-12 | 河北工业大学 | Hydrophilic functional carbon sphere and application thereof for removing heavy metal ions in waste water |
| CN104525103A (en) * | 2014-12-31 | 2015-04-22 | 中国地质大学（武汉） | Magnetic iron oxide/sepiolite nanocomposite and preparation method and application thereof |
-
2015
- 2015-09-10 CN CN201510574057.7A patent/CN105126757A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031415A (en) * | 1999-07-19 | 2001-02-06 | Kagawaken Sangyo Gijutsu Shinko Zaidan | Porous molded article based on calcium silicate or silica |
| CN103055806A (en) * | 2011-10-18 | 2013-04-24 | 中国科学技术大学 | Carbon-coated attapulgite clay composite material and its preparation method |
| CN102600801A (en) * | 2012-04-09 | 2012-07-25 | 西北师范大学 | Preparation of waste potato residue/palygorskite composite adsorbent and application of adsorbent in treatment of potato starch processing wastewater |
| CN103157438A (en) * | 2013-04-10 | 2013-06-19 | 哈尔滨工业大学 | Preparation method of carbon microsphere/nanometer iron oxide magnetic composite material |
| CN103623779A (en) * | 2013-12-06 | 2014-03-12 | 河北工业大学 | Hydrophilic functional carbon sphere and application thereof for removing heavy metal ions in waste water |
| CN104525103A (en) * | 2014-12-31 | 2015-04-22 | 中国地质大学（武汉） | Magnetic iron oxide/sepiolite nanocomposite and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| DAN LI等: "An investigation into formation mechanism of amorphous hierarchical porous carbons by diatomite as template：Effect of furfuryl alcohol and glucose", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEER》 * |
| JOZSEF DOBOR等: "A new carbonediatomite earth composite adsorbent for removal of heavy metals from aqueous solutions and a novel application idea", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311147A (en) * | 2016-10-17 | 2017-01-11 | 中国矿业大学(北京) | Illite loaded nanocarbon compound adsorbing material and preparation method thereof |
| CN107042085A (en) * | 2016-10-17 | 2017-08-15 | 中国矿业大学(北京) | A kind of oxygen-enriched functional group's carbon/illite composite adsorbent material and preparation method thereof |
| CN106946357A (en) * | 2017-05-08 | 2017-07-14 | 宁波市川宁环保科技有限公司 | A kind of preparation method for the filler special for artificial wetland fixed for microorganism |
| CN106946357B (en) * | 2017-05-08 | 2020-09-25 | 宁波市川宁环保科技有限公司 | Preparation method of constructed wetland special filler for microbial immobilization |
| CN109652022A (en) * | 2018-12-28 | 2019-04-19 | 青海大学 | A kind of preparation method of NEW TYPE OF COMPOSITE diatomite phase-changing energy storage material carrier |
| CN109652022B (en) * | 2018-12-28 | 2020-07-03 | 青海大学 | Preparation method of novel composite diatomite phase change energy storage material carrier |
| CN110354582A (en) * | 2019-06-27 | 2019-10-22 | 重庆中轻装备有限公司 | A kind of soy sauce filtration process |
| CN110270309A (en) * | 2019-07-25 | 2019-09-24 | 西南石油大学 | A kind of shale gas fracturing outlet liquid water treatment absorbent preparation method and application |
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Inventor after: Sun Zhiming Inventor after: Li Ke Inventor after: Zheng Shuilin Inventor after: Yao Guangyuan Inventor before: Sun Zhiming Inventor before: Zheng Shuilin Inventor before: Yao Guangyuan Inventor before: Li Chunquan |
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Application publication date: 20151209 |