CN105688847B - A kind of gelatin/flyash composite adsorbing material and preparation method thereof - Google Patents
A kind of gelatin/flyash composite adsorbing material and preparation method thereof Download PDFInfo
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- CN105688847B CN105688847B CN201610138423.9A CN201610138423A CN105688847B CN 105688847 B CN105688847 B CN 105688847B CN 201610138423 A CN201610138423 A CN 201610138423A CN 105688847 B CN105688847 B CN 105688847B
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- gelatin
- flyash
- dialdehyde
- composite adsorbing
- adsorbing material
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of gelatin/flyash composite adsorbing material of present invention offer and preparation method thereof.This method is particle-filled dose of absorption with the flyash that γ aminopropyl triethoxysilanes are modified, adds cross-linked modifier after mixing, a kind of gelatin/flyash composite adsorbing material is prepared by cross-linking modified using gelatin as base material.Gelatin prepared by the present invention/flyash composite adsorbing material not only has stronger pollutant adsorption effect, but also degraded by environment, therefore can be used as fertilizer without generating secondary pollution after its absorption pollutant.The raw material sources of the sorbing material are extensive, while the recycling for process hides hide offal and waste coal slag provides new way.To sum up, the novel absorption material that prepared by the present invention has good market application value and foreground.
Description
Technical field
The present invention relates to sorbing material fields, and in particular to a kind of gelatin that absorption property is good/flyash composite adsorption material
Material and preparation method thereof.
Background technology
Current China's economic development is rapid, and shortage of resources and environmental pollution are to develop the two large problems faced at present.Especially
The pollution and shortage of its water resource, it is even more the living or death concerning the mankind not only to influence economic development.Water pollution problems is solved, not only may be used
To provide more water resources, additionally it is possible to be further reduced environmental pollution.
At present for the improvement of water pollution, in addition to traditional sedimentation, using it is more be membrane filter method.Sedimentation efficiency
Low consumption duration, membrane filter method need to consume more power, and need constantly to remove filter cake, regularly replace filter medium, hold
Easily cause secondary pollution.And the advantages such as absorption method has and has a wide range of application, and does not consume power, and treating capacity is big.
Flyash is the flying dust after the coal combustion captured in the flue gas that coal-fired firepower electrical plant discharges, it is by SiO2、
Al2O3The porous beads of equal inorganic components composition, grain size has large specific surface area between 0.8-300 μm, thus has good
Absorption property.It is adsorbed, is had some limitations using flyash.Since the grain size of flyash is small, adsorb in water
When be easy to happen moiety aggregation, bad dispersibility.Recycling after fly ash absorbent adsorbs in aqueous solution simultaneously is also relatively difficult,
The mode for often requiring to use filtering increases the cost and complexity of water process.
Product of the gelatin as the collagen partial hydrolysis in animal tissue, derives from a wealth of sources.Being freeze-dried gelatin can be with
Obtain the porous spongy material with good absorption property.But due to the water-wet behavior of gelatin, when of short duration in water
Between will dissolve.
The present invention is prepared for a kind of gelatin/flyash composite adsorbing material using fly ash micro-sphere and gelatin as raw material, by powder
Coal ash surface grafting has the coupling agent of amino, by dialdehyde crosslinking agent by gelatin and amination modified flyash, gelatin with
Gelatin crosslinking is got up so that fly ash micro-sphere is uniformly dispersed in gelatin gel, and a kind of high absorption is obtained after freeze-drying
The degradable cationic gelatin/flyash composite adsorbing material of performance.Gelatin/flyash composite adsorbing material immerses sewage
Afterwards, the cationic pollutant in external cross-linking modified porous gelatin absorption water, while stable gel is gradually formed, dry
Fly ash micro-sphere promotes water to spreading inside it in inside, and further Liquidity limit pollutant accelerates pollutant in gel
In inner diffusing rate, increase adsorbance.
Invention content
In order to improve the dispersibility of fly ash absorbent and the stability of gelatin adsorption material, the present invention uses coupling agent
Modified coal ash surface obtains amination modified flyash, uses dialdehyde cross-linking agents gelatin and amination modified fine coal
A kind of novel composite adsorbing material has been made to improve the stability and adsorption effect of adsorbent in ash.
The invention is realized by the following technical scheme, and unless otherwise indicated, involved number is parts by weight, percentage
Than being weight percentage.
The present invention provides a kind of composite adsorbing material, and preparation method is as follows：
(1) 1 part of flyash is 3-5 hours dry at 110-180 DEG C, 30-60 parts of organic solution high speed stirrings are added
5-10 minutes.0.5-3 parts of coupling agent is added dropwise.Return stirring 5-10 hours at 60-90 DEG C, decompression filters, by filter cake
It is dried at 100-120 DEG C, ball mill 200-600r/min is ground 10-30 minutes;
(2) gelatin is dissolved in the mass concentration of 1%-10% in 40-80 DEG C of water, is added accounts for gelatin under high velocity agitation
The amination modified flyash of dry weight 1%-20%, the dialdehyde crosslinking agent for being stirring evenly and then adding into 1%-10% obtain gelatin/fine coal
Grey plural gel；
(3) mold will be poured into after above-mentioned matrix solution deaeration, freeze-drying obtains the spongiform compound suction of gelatin/flyash
Enclosure material;
(4) gelatin/flyash composite adsorbing material is put into sink in sewage in the netted bracket of hard and is adsorbed.
The reaction dissolvent of amination modified flyash described in above-mentioned technology case be benzene,toluene,xylene and methanol,
One or more of ethyl alcohol mixed organic solvents.
The coupling agent that amination modified flyash described in above-mentioned technology case uses is gamma-aminopropyl-triethoxy silicon
Alkane.
Gelatin described in above-mentioned technology case is crosslinked the dialdehyde crosslinking agent used with amination modified flyash and is：Dialdehyde
Any one or a few in starch, dialdehyde cellulose, dialdehyde Propiram, dialdehyde guar gum glutaraldehyde, dialdehyde polyethylene glycol.
The ratio dry weight of flyash and gelatin described in above-mentioned technology case is 1:(5~100).
The present invention compared with the prior art, have the advantages that various good effects and, can inductive generalization it is as follows：
(1) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, base stock are work
Industry waste, absorption property is strong, can be good at the adsorbent for substituting organic synthetic resin type, can voluntarily biology be dropped after absorption
Solution, is a kind of high-efficiency adsorbent of environment friendly；
(2) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, uses silane coupling agent
Modified fly ash micro-sphere surface obtains amination modified fly ash micro-sphere, increases its reactivity, is crosslinked with gelatin；
(3) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, not only improves powder
Dispersibility of the coal ash in sewage, improves its adsorption efficiency, and facilitates recycling to adsorbent after absorption, extends its application
Range；
(4) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof improves gelatin suction
Attached dose of mechanical performance, the crosslinking with amination modified flyash enhance its stability in aqueous solution, extend it and answer
Use range；
(5) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, in adsorption process,
The larger organic substance that can adsorb macromolecular in aperture of outer gelatin reticulated absorbent, the flyash aperture of inner aperture diameter are small
Large specific surface area can adsorb the small molecular ion of solubilised state, avoid flyash and be directly exposed to surface micropore quilt in sewage
Macromolecular substances block；
(6) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, can be used as after absorption
Fertilizer, the organic principle in gelatin and sewage can use the nitrogen content increased in soil, flyash that can change the gas permeability of soil；
(7) a kind of gelatin/flyash composite adsorbing material provided by the invention and preparation method thereof, base stock can
To be all originated from industrial waste, derive from a wealth of sources, it is cheap, there is potential economic benefit, conducive to being widely used.
Specific implementation method
Three embodiments of the present invention are given below, the present invention is specifically described by embodiment.It is necessary to herein
, it is noted that embodiment is served only for that the present invention is further detailed, it should not be understood as the limit to the scope of the present invention
System, the person skilled in the art in the field can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
In the following example, unless otherwise indicated, involved number is parts by weight, and percentage is weight percent
Than.
Embodiment 1
1 part of flyash is 5 hours dry at 110 DEG C, 20 parts of benzene high speeds are added and stir 5 minutes.It is added dropwise 0.9 part
Coupling agent.Return stirring 1 hour at 60 DEG C, decompression are filtered, filter cake are dried at 120 DEG C, ball mill 200r/min is ground
Mill 10 minutes.Gelatin is dissolved in 2% mass concentration in 40 DEG C of water, the amino of 1% mass concentration is added under high velocity agitation
Change modified flyash, be stirring evenly and then adding into 1% dialdehyde starch crosslinked dose obtains gelatin/flyash plural gel；It will be above-mentioned
Mold is poured into after matrix solution deaeration, is freeze-dried 12 hours, is obtained spongiform gelatin/flyash composite adsorbing material.It will
Gelatin/flyash composite adsorbing material is put into sink in sewage in the netted bracket of hard and be adsorbed.
Embodiment 2
1 part of flyash is 3 hours dry at 120 DEG C, 15 parts of toluene are added and 15 parts of ethyl alcohol high speeds stir 7 minutes.
2 parts of coupling agent is added dropwise.Return stirring 10 hours at 90 DEG C, decompression are filtered, filter cake are dried at 110 DEG C, ball milling
Machine 600r/min is ground 15 minutes.Gelatin is dissolved in 2% mass concentration in 40 DEG C of water, 1% matter is added under high velocity agitation
The amination modified flyash for measuring concentration, being stirring evenly and then adding into 2% dialdehyde guar gum, to obtain gelatin/flyash compound solidifying
Glue；Mold will be poured into after above-mentioned matrix solution deaeration, is freeze-dried 15 hours, is obtained the spongiform compound suction of gelatin/flyash
Enclosure material.Gelatin/flyash composite adsorbing material is put into sink in sewage in the netted bracket of hard and is adsorbed.
Embodiment 3
1 part of flyash is 4 hours dry at 170 DEG C, 5 parts of dimethylbenzene are added and 10 parts of methanol high speeds stir 7 minutes.
1 part of coupling agent is added dropwise.Return stirring 8 hours at 80 DEG C, decompression are filtered, filter cake are dried at 108 DEG C, ball mill
500r/min is ground 18 minutes.Gelatin is dissolved in 7% mass concentration in 70 DEG C of water, 5% mass is added under high velocity agitation
The amination modified flyash of concentration, the dialdehyde guar gum for being stirring evenly and then adding into 7% obtain gelatin/flyash plural gel；
Mold will be poured into after above-mentioned matrix solution deaeration, is freeze-dried 24 hours, is obtained spongiform gelatin/flyash composite adsorption material
Material.Gelatin/flyash composite adsorbing material is put into sink in sewage in the netted bracket of hard and is adsorbed.
Claims (3)
1. a kind of gelatin/flyash composite adsorbing material, it is characterised in that using gelatin as base material, with amination modified flyash
For particle-filled dose of absorption, by the cross-linking modified preparation of dialdehyde polysaccharide, specific preparation method is as follows：
(1) flyash of 1 part of drying 3-5 hours at 110-180 DEG C is taken, high-speed stirred 5- after 30-60 parts of organic solvents is added
10 minutes, 0.5-3 parts of gamma-aminopropyl-triethoxy-silane is added dropwise at room temperature, it is then that mixture is anti-at 60-90 DEG C
It answers 5-10 hours, decompression filters, and later dries filter cake at 100-120 DEG C and is ground in 200-600r/min using ball mill
10-30 minutes, amination modified flyash is prepared；
(2) gelatin is dissolved in deionized water, obtains the gelatin solution of a concentration of 1%-10%, is added under high velocity agitation later
The amination modified flyash of gelatin dry weight 1-20% is accounted for, is stirred under the conditions of 40 DEG C 1-2 hours, is then added and accounts for gelatin dry weight
The crosslinking agent of 1%-10%, continuation are stirred 0.5-2 hours under the conditions of 40 DEG C, are then poured into mixed liquor quiet at room temperature in mold
It sets 1-3 hours, finally freeze-drying obtains gelatin/flyash composite adsorbing material.
2. gelatin according to claim 1/flyash composite adsorbing material, it is characterised in that amination modified flyash
The organic solvent used in preparation process is any one or a few the mixing in benzene,toluene,xylene, methanol and ethyl alcohol
Object.
3. gelatin according to claim 1/flyash composite adsorbing material, it is characterised in that the crosslinking agent used is dialdehyde
Xanthans, dialdehyde starch, dialdehyde carboxymethyl cellulose, dialdehyde pulullan polysaccharide, dialdehyde sodium alginate, dialdehyde Weilan gum, dialdehyde
Any one or a few mixture in guar gum.
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| CN105688847B true CN105688847B (en) | 2018-08-14 |
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| CN106925236B (en) * | 2017-03-28 | 2019-05-14 | 武汉轻工大学 | A kind of gelatin-manganese dioxide composites preparation method and applications for adsorbing heavy metal |
| CN107335495A (en) * | 2017-06-08 | 2017-11-10 | 全椒县崇明米业有限公司 | A kind of big rice processing method for reducing content of cracking rice |
| CN107149958A (en) * | 2017-06-08 | 2017-09-12 | 全椒县崇明米业有限公司 | A kind of big rice processing method for reducing impurity |
| CN107489073A (en) * | 2017-08-24 | 2017-12-19 | 浙江科屹耐火材料有限公司 | A kind of environmental-protection fireproof wallpaper and preparation method thereof |
| CN108633634B (en) * | 2018-04-03 | 2022-09-02 | 黎昊源生物工程(山东)股份有限公司 | Method for cultivating crops in moderate and severe saline-alkali soil |
| CN108927117A (en) * | 2018-08-02 | 2018-12-04 | 深圳市深港产学研环保工程技术股份有限公司 | A kind of preparation method of flyash-sodium alginate composite adsorbing material |
| CN109078622A (en) * | 2018-10-16 | 2018-12-25 | 齐鲁工业大学 | A kind of gelatin-based both sexes micro-sphere absorption material and preparation method thereof |
| CN113735240A (en) * | 2021-08-26 | 2021-12-03 | 天津赞兰科技有限公司 | Nitrogen removal product for aquaculture and preparation method thereof |
| CN115583854A (en) * | 2022-10-25 | 2023-01-10 | 中国科学院生态环境研究中心 | Method for preparing water-fertilizer integrated material from fly ash |
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| JPS5278687A (en) * | 1975-12-25 | 1977-07-02 | Nagasaki Prefecture | Manufacture of heavy metal collecting agents as main material of fly ash |
| CN101700491B (en) * | 2009-11-09 | 2011-07-20 | 中国海洋石油总公司 | Method for modifying fly ash |
| CN103013138B (en) * | 2012-12-11 | 2014-10-15 | 四川大学 | Gelatin-based nano-composite material and preparation method thereof |
| CN103071465B (en) * | 2013-01-14 | 2015-06-17 | 太原理工大学 | Preparation method of spherical polymerized micron-size flyash particles |
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