CN105642233B - A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons - Google Patents
A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons Download PDFInfo
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- CN105642233B CN105642233B CN201610002608.7A CN201610002608A CN105642233B CN 105642233 B CN105642233 B CN 105642233B CN 201610002608 A CN201610002608 A CN 201610002608A CN 105642233 B CN105642233 B CN 105642233B
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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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
Being prepared the invention discloses a kind of serialization has the sodium carboxymethylcellulose of pollutant absorption and drug slow release function（CMC）/ graphene oxide（GO）The method of composite hydrogel microballoon, this method is mainly by solution blending by a certain proportion of CMC, GO and citric acid（CA, crosslinking agent）It is scattered in deionized water, CMC/GO complex microspheres is then prepared by spray drying process.Prepared complex microsphere has good swelling behavior, can adsorb the organic dyestuff and heavy metal ion in industrial wastewater, maximal absorptive capacity is respectively 66 mg/g（Eosin Y）、120 mg/g（Cr6+）.Meanwhile the complex microsphere also acts as sustained-release drug carrier.The present invention prepares CMC/GO composite hydrogel microballoons by spray drying, simple for process, is suitable for industrialization large-scale production, has good market application prospect in terms of broad spectrum type adsorbent and sustained-release drug carrier.
Description
Technical field
The present invention relates to sewage disposals and medicament slow release field more particularly to one kind can adsorbing organic dyestuff but also absorption
The preparation method of the CMC/GO composite hydrogel microballoons of heavy metal ion.
Background technology
In recent years, the fast development of petrochemical industry produces a large amount of industrial wastewater, wherein containing a large amount of acid,
Alkali, salt, organic solvent, toxic dye and heavy metal ion etc. constitute grave danger to the health of ecological environment and the mankind.For
It solves the above problems, researchers have turned one's attention to natural macromolecular material, because it is with good biocompatibility
And it has no toxic side effect, it is often more important that, they are renewable resources.It is more serious in fossil resources increasingly depleted, environmental pollution
Today, advantage of the natural macromolecular material in terms of water process gradually highlight.
Cellulose is a kind of natural macromolecular material that content is most abundant in nature, frequent by the hydrogel prepared by it
Applied to biomedicine field.However, since such hydrogel lacks active group, make its to the absorption property of pollutant compared with
Difference, the rate of adsorption are relatively low.In order to improve above-mentioned condition, some researchers by by cellulose derivative and inorganic matter it is compound come
Improve its performance.As Chinese patent CN104801286A disclose hydroxypropyl cellulose/GO composite hydrogels preparation method and
It is applied, and the composite hydrogel of 8 wt%GO of invention is to methylene blue（MB）Maximal absorptive capacity be 12 mg/g, it is purer
3 mg/g of hydroxy propyl cellulose hydrogel improve 300%.Nevertheless, there is also adsorb kind to pollutant for such hydrogel
Class is single, is difficult to the problem of large-scale production, such as document and Chinese patent：Journal of Applied Polymer
Science, 22,41101; Water Res, 2004, 38, 2643-2650; CN104437410A.And in industrial wastewater
Pollutant load it is complex, in addition to organic dyestuff, also heavy metal ion etc..Therefore, exploitation one kind can be adsorbed a variety of
Pollutant（Including organic dyestuff and heavy metal ion）Broad spectrum type adsorbent be the field a major challenge.
On the other hand, feed liquid is exactly atomized into droplet by spray drying through atomizer, and by directly being connect with hot gas
It touches and obtains a drying process of powder.Institute's jetting liquid can be emulsion or suspension, can also be molten liquid.Control is closed
Powder, particle or hollow ball can be made in product by suitable condition.Compared to the method that other prepare microballoon, the advantage of spray drying
It is very prominent：Easy to operate, condition is easy to control；Hothouse has certain negative pressure, ensure that the cleaning of dry environment, product do not have
Pollution, the purity and quality of product are higher；Be conducive to large-scale continuous production, production efficiency is high.
Invention content
In order to overcome above-mentioned deficiency in the prior art, the present invention provides one kind have it is simple to operation, without organic
Solvent does not need emulsifier yet, and the purity and quality of products obtained therefrom are higher, and obtained hydrogel microsphere is to organic dyestuff and again
The method that metal ion has the CMC/GO composite hydrogel microballoons of excellent absorption property.
The object of the present invention is achieved like this：
A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons, includes the following steps：
（1）Graphene oxide prepared by Hummers methods is scattered in deionized water, ultrasound stripping obtains the outstanding of GO
Supernatant liquid；
（2）CMC is dissolved in deionized water, 60 °C of lower constant temperature stirrings obtain CMC aqueous solutions；
（3）CA is dissolved in deionized water, CA aqueous solutions are obtained；
（4）GO suspension in step 1, it is total that the CA aqueous solutions in CMC aqueous solutions and step 3 in step 2 carry out solution
It is mixed, prepare CMC/GO/CA mixtures；
（5）It is micro- that the mixture of CMC/GO/CA in step 4 by spray dryer is prepared into CMC/GO composite hydrogels
Ball.
The mass concentration of GO aqueous solutions is 2/ in the step 1（1~10）g/L.
The mass concentration of CMC aqueous solutions is 3/ in the step 2（1~10）g/L.
The mass concentration of CA aqueous solutions is 3/ in the step 3（1~10）g/L.
CMC in CMC/GO aqueous solutions in the step 4：GO：The mass ratio of CA is 1~10：1~100：1~50；
Composite hydrogel microballoon is prepared using spray drying process, chemical reaction occurs in spray-drying process and forms friendship
Connection；Spray drying parameters are arranged in the step 5, and 70~150 °C of inlet temperature, sample size 10~80%, air mass flow 10~
80%；
Prepared hydrogel microsphere can be used in the absorption of organic dyestuff and heavy metal ion and drug in industrial wastewater
Sustained release release.
Positive beneficial effect：The present invention prepares CMC/GO composite hydrogel microballoon this method by spray drying process has letter
It is single easy to operate, it is not necessarily to organic solvent, does not also need emulsifier, the purity and quality of products obtained therefrom are higher, and present invention introduces than table
Area is big and carries multi-functional GO, has good swelling behavior, improves adsorption capacity of the product to dyestuff；The present invention
CMC/GO composite hydrogel microballoons to organic dyestuff（MB and Eosin Y）There is excellent absorption property with heavy metal ion,
Its maximal absorptive capacity is respectively 66 mg/g（Eosin Y）、120 mg/g（Cr6+）.Meanwhile the complex microsphere also acts as slow releasing medicinal
Object carries；The CMC/GO composite hydrogel microballoons of the present invention are to various heavy.The present invention prepares CMC/GO by spray drying and answers
Heshui gel micro-ball, it is simple for process, it is suitable for industrialization large-scale production, in terms of broad spectrum type adsorbent and sustained-release drug carrier
With good market application prospect.
Description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepared by CMC/GO composite hydrogel microballoons before spray drying after Fu in
Leaf transformation is infrared（FT-IR）Spectrogram；
Fig. 2 is scanning electron microscope (SEM) figure of the CMC/GO composite hydrogel microballoons prepared by the embodiment of the present invention 1；
Fig. 3 is the CMC/GO composite hydrogels microballoon prepared by the embodiment of the present invention 1 to organic dyestuff MB（Cationic contaminates
Material）With Eosin Y（Anionic dyes）And the histogram of the adsorbance of metal ion Cu2+, Cr6+, Cd2+, Pb2+.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is described further：
A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons, includes the following steps：
（1）Graphene oxide prepared by Hummers methods is scattered in deionized water, ultrasound stripping obtains the outstanding of GO
Supernatant liquid；
（2）CMC is dissolved in deionized water, 60 °C of lower constant temperature stirrings obtain CMC aqueous solutions；
（3）CA is dissolved in deionized water, CA aqueous solutions are obtained；
（4）GO suspension in step 1, it is total that the CA aqueous solutions in CMC aqueous solutions and step 3 in step 2 carry out solution
It is mixed, prepare CMC/GO/CA mixtures；
（5）It is micro- that the mixture of CMC/GO/CA in step 4 by spray dryer is prepared into CMC/GO composite hydrogels
Ball.
The mass concentration of GO aqueous solutions is 2/ in the step 1（1~10）g/L.
The mass concentration of CMC aqueous solutions is 3/ in the step 2（1~10）g/L.
The mass concentration of CA aqueous solutions is 3/ in the step 3（1~10）g/L.
CMC in CMC/GO aqueous solutions in the step 4：GO：The mass ratio of CA is 1~10：1~100：1~50；
Composite hydrogel microballoon is prepared using spray drying process, chemical reaction occurs in spray-drying process and forms friendship
Connection；Spray drying parameters are arranged in the step 5, and 70~150 °C of inlet temperature, sample size 10~80%, air mass flow 10~
80%；
Prepared hydrogel microsphere can be used in the absorption of organic dyestuff and heavy metal ion and drug in industrial wastewater
Sustained release release.
Embodiment 1
The present embodiment prepares CMC/GO composite hydrogel microballoons as follows first：
（1）Prepare CMC/GO/CA mixed solutions
Graphite oxide ultrasound stripping prepared by Hummers methods is scattered in deionized water, a certain amount of CMC is then removed
It is soluble in water with CA difference, the mixture of CMC/GO/CA is being obtained by solution blending, the wherein content of graphene oxide is 8
wt%；
（2）CMC/GO composite hydrogel microballoons are prepared by spray drying
Suitable inlet temperature, sample size, air mass flow are set, CMC/GO compound water congealings are prepared by spray dryer
Glue microballoon, because temperature is higher in spray-drying process, it is anti-that esterification occurs for-the COOH on the-OH and CMC on crosslinking agent CA
It answers；
Fig. 1 is infrared before and after the CMC/GO composite hydrogels in the embodiment of the present invention 1 are micro-sphere crosslinked（FT-IR）Spectrum
Figure.It can be seen that complex microsphere is before crosslinking, 3424 cm-1、3000 cm-1Place is the stretching vibration of-OH in CMC structure unit
Absorption peak.FT-IR spectral lines after crosslinking are in 1740 cm-1Place has more the characteristic absorption peak an of-COOR, and in 3424 cm-1
The characteristic absorption peak of-the OH at place obviously weakens, and shows-the COOH and crosslinking agent on the CMC in CMC/GO composite hydrogel microballoons
- OH on CA, which has occurred, has been cross-linked to form ester hydroxyl.
Fig. 2 is the scanning electron microscope of the CMC/GO composite hydrogel microballoons prepared by the embodiment of the present invention 1（SEM）Figure.It can be with
Find out：CMC/GO composite hydrogel microballoon monodispersities are good, and the grain size of microballoon is 3 μm or so.
Fig. 3 is the CMC/GO composite hydrogels microballoon prepared by the embodiment of the present invention 1 to organic dyestuff MB（Cationic contaminates
Material）With Eosin Y（Anionic dyes）And metal ion Cu2+、Cr6+、Cd2+、Pb2+Adsorbance histogram.All dirts
The initial concentration for contaminating object is 200 mg/L, 15 °C of test temperature.As a result it shows：Composite hydrogel microballoon is to MB and Eosin Y
Maximal absorptive capacity respectively reached 60 and 66 mg/g；In addition, it is to Cu2+、Cr6+、Cd2+、Pb2+Maximal absorptive capacity reach respectively
To 94,120,101 and 85 mg/g.The above results show that CMC/GO has metal ion and organic dyestuff excellent suction
Attached ability can be used for the processing of industrial wastewater.
Embodiment 2
The present embodiment 2 prepares CMC/GO composite hydrogel microballoons by 1 identical mode of embodiment, differs only in step 1
2 wt%. of middle graphene oxide
After tested, the CMC/GO composite hydrogels microballoon obtained by the present embodiment is to metal ion Cu2+、Cr6+、Cd2+、Pb2+'s
Adsorbance is respectively the adsorbance difference of 38 mg/g, 45 mg/g, 41 mg/g and 37 mg/g. organic dyestuff MB and Eosin Y
For 28 mg/g and 29 mg/g.
Embodiment 3
The present embodiment 3 prepares CMC composite hydrogel microballoons by 1 identical mode of embodiment, differs only in oxygen in step 1
4 wt%. of graphite alkene
After tested, the CMC/GO composite hydrogels microballoon obtained by the present embodiment is to metal ion Cu2+、Cr6+、Cd2+、Pb2+'s
Adsorbance is respectively 59 mg/g, 76 mg/g, 59 mg/g and 49 mg/g.The adsorbance of organic dyestuff MB and Eosin Y are distinguished
For 39 mg/g and 41 mg/g.
Embodiment 4
The present embodiment 4 prepares CMC/GO composite hydrogel microballoons by 1 identical mode of embodiment, differs only in step 1
6 wt% of middle GO.
After tested, the CMC/GO composite hydrogels microballoon obtained by the present embodiment is to metal ion Cu2+、Cr6+、Cd2+、Pb2+'s
Adsorbance is respectively 71 mg/g, 99 mg/g, 71 mg/g and 61 mg/g.The adsorbance of organic dyestuff MB and Eosin Y are distinguished
For 51 mg/g and 54 mg/g.
The present invention by spray drying process prepare CMC/GO composite hydrogel microballoon this method have it is simple to operation, be not necessarily to
Organic solvent does not need emulsifier yet, and the purity and quality of products obtained therefrom are higher, present invention introduces large specific surface area and with more
The GO of functional group has good swelling behavior, improves adsorption capacity of the product to dyestuff；The CMC/GO Compound Waters of the present invention
Gel micro-ball is to organic dyestuff（MB and Eosin Y）There is excellent absorption property, maximal absorptive capacity point with heavy metal ion
It Wei not 66 mg/g（Eosin Y）、120 mg/g（Cr6+）.Meanwhile the complex microsphere also acts as slow releasing pharmaceutical load；The present invention's
CMC/GO composite hydrogel microballoons are to various heavy.The present invention prepares CMC/GO composite hydrogel microballoons by spray drying,
It is simple for process, it is suitable for industrialization large-scale production, there is good city in terms of broad spectrum type adsorbent and sustained-release drug carrier
Field application prospect.
The above case study on implementation is merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, the field those of ordinary skill within the scope of knowledge, within the spirit and principles in the present invention made by it is any
Modification, equivalent substitute and improvement etc., are regarded as the protection domain of the application.
Claims (6)
1. a kind of method that continuity method prepares CMC/GO composite hydrogel microballoons, which is characterized in that include the following steps：
（1）Graphene oxide prepared by Hummers methods is scattered in deionized water, ultrasound stripping obtains the suspension of GO；
（2）CMC is dissolved in deionized water, 60 °C of lower constant temperature stirrings obtain CMC aqueous solutions；
（3）Citric acid CA is dissolved in deionized water, citric acid CA aqueous solutions are obtained；
（4）By step（1）In GO suspension, step（2）In CMC aqueous solutions and step（3）In citric acid CA aqueous solutions
Solution blending is carried out, CMC/GO/CA mixtures are obtained；
（5）By step（4）In the mixture of CMC/GO/CA by spray dryer to prepare CMC/GO composite hydrogels micro-
Ball.
2. the method that a kind of continuity method according to claim 1 prepares CMC/GO composite hydrogel microballoons, it is characterised in that：
The step（1）The mass concentration of middle GO suspension is 2/（1~10）g/L.
3. the method that a kind of continuity method according to claim 1 prepares CMC/GO composite hydrogel microballoons, it is characterised in that：
It is characterized in that：The step（2）The mass concentration of middle CMC aqueous solutions is 3/（1~10）g/L.
4. the method that a kind of continuity method according to claim 1 prepares CMC/GO composite hydrogel microballoons, it is characterised in that：
It is characterized in that：The step（3）The mass concentration of middle citric acid CA aqueous solutions is 3/（1~10）g/L.
5. the method that a kind of continuity method according to claim 1 prepares CMC/GO composite hydrogel microballoons, it is characterised in that：
The step（4）CMC in middle CMC/GO/CA mixtures：GO：The mass ratio of CA is 1~10：1~100：1~50.
6. a kind of continuity method according to claim 1 prepares the water-setting prepared by the method for CMC/GO composite hydrogel microballoons
Glue microballoon is used for the sustained release of the absorption of organic dyestuff and heavy metal ion and drug release in industrial wastewater.
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| CN106317433A (en) * | 2016-08-13 | 2017-01-11 | 齐齐哈尔大学 | Preparation method of flax-bit-based carboxymethylcellulose and graphene oxide composite film |
| CN106492761A (en) * | 2016-11-01 | 2017-03-15 | 河南工业大学 | A kind of preparation method of magnetic hydrogel microsphere |
| CN108262020A (en) * | 2016-12-30 | 2018-07-10 | 海门市源美美术图案设计有限公司 | Biomass modified graphite oxide and the application in terms of uranium improvement |
| CN107973920A (en) * | 2017-11-15 | 2018-05-01 | 深圳大学 | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof |
| CN108148224B (en) * | 2017-12-12 | 2021-05-28 | 明基材料有限公司 | Graphene/cellulose composite aerogel and manufacturing method thereof |
| CN108393071A (en) * | 2018-03-21 | 2018-08-14 | 广东电网有限责任公司电力科学研究院 | A kind of compound adsorbent and preparation method thereof |
| CN108948228A (en) * | 2018-06-22 | 2018-12-07 | 福建省绿麒食品胶体有限公司 | A kind of method that spray drying prepares Phosphation agar |
| CN108620045A (en) * | 2018-07-11 | 2018-10-09 | 河南科技大学 | A kind of preparation method of graphene-based PEI-mGO/CMC/PVA three-dimensional composite materials |
| CN111939878A (en) * | 2020-08-28 | 2020-11-17 | 陕西科技大学 | Ternary composite aerogel and preparation method and application thereof |
| CN112044417A (en) * | 2020-09-16 | 2020-12-08 | 王宇 | Adsorbing material for treating printing and dyeing wastewater and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649045A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院兰州化学物理研究所 | Method for preparing attapulgite clay composite gel adsorption microsphere by spray drying |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN103877953A (en) * | 2014-03-30 | 2014-06-25 | 河南城建学院 | Hydrogel for sewage treatment as well as preparation method thereof |
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| CN105175750A (en) * | 2015-09-10 | 2015-12-23 | 河南工业大学 | Preparation method of aquagel microspheres |
-
2016
- 2016-01-06 CN CN201610002608.7A patent/CN105642233B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649045A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院兰州化学物理研究所 | Method for preparing attapulgite clay composite gel adsorption microsphere by spray drying |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
| CN103877953A (en) * | 2014-03-30 | 2014-06-25 | 河南城建学院 | Hydrogel for sewage treatment as well as preparation method thereof |
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| CN105175750A (en) * | 2015-09-10 | 2015-12-23 | 河南工业大学 | Preparation method of aquagel microspheres |
Non-Patent Citations (1)
| Title |
|---|
| 纤维素微球的研究进展;吴伟兵等;《纤维素科学与技术》;20130630;第21卷(第2期);79-86 * |
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