CN106334539A - Cationic polymer modified montmorillonoid adsorbent and preparation method thereof - Google Patents
Cationic polymer modified montmorillonoid adsorbent and preparation method thereof Download PDFInfo
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- CN106334539A CN106334539A CN201610870739.7A CN201610870739A CN106334539A CN 106334539 A CN106334539 A CN 106334539A CN 201610870739 A CN201610870739 A CN 201610870739A CN 106334539 A CN106334539 A CN 106334539A
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- solution
- coupling agent
- cationic polymer
- montmorillonite
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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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
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a cationic polymer modified montmorillonoid adsorbent which is characterized being prepared by the following steps: in a 90% alcohol solution, slowly dropping an amino silane coupling agent, adjusting the pH value to be 3-4 by using acetic acid at the same time, and after dropping, continuously stirring till the solution is transparent so as to obtain a 0.1-3% amino silane coupling agent solution for later use; weighing the prepared amino silane coupling agent solution, adding montmorillonoid, stirring for 30-60 minutes at the room temperature, filtering, drying filter cakes for 1-3 hours at 50-60 DEG C, performing a constant-temperature drying reaction for 1-2 hours at 120 DEG C, and cooling so as to obtain amino silane coupling agent modified montmorillonoid; uniformly mixing the prepared amino silane coupling agent modified montmorillonoid with a poly-epoxy chloropropane-dimethylamine cationic polymer solution with alkali end groups as epoxy groups, drying at 50-60 DEG C till being constant in weight, taking out the material, and crushing, thereby obtaining the cationic polymer modified montmorillonoid adsorbent. Desorption decoloring tests show that compared with montmorillonoid, the cationic polymer modified montmorillonoid adsorbent is remarkably improved in adsorption decoloring property on organic dyes.
Description
Technical field
The present invention relates to a kind of cation adsorbing material, more particularly to one kind are processed with printing and dyeing industrial waste water for dyestuff
Cation-modified montmorillonite sorbent and preparation method thereof.
Background technology
Up to more than 70 ten thousand tons of the annual production of whole world organic dyestuff, wherein about 12% dyestuff is in production and application process
In be discharged in the way of colorful wastewater.Due to waste water from dyestuff complicated components, colourity is deep and cod and bod value is of a relatively high,
Directly discharge will necessarily cause severe contamination to environment, therefore needs before discharging to carry out wastewater treatment.Common dyes waste water
Processing method mainly includes flocculence, oxidizing process, bioanalysis, absorption method etc., and wherein, the sludge quantity that flocculence produces is big and is dehydrated
Difficulty, Treatment of Sludge operating cost is high, and easily causes secondary pollution；Oxidizing process energy consumption is larger, and cod clearance is relatively low；Biological
Method has certain requirement to conditions such as the ph of waste water from dyestuff, temperature it is difficult to adapt to that variation water quality is big, kind of dyes is many, toxicity is high
Waste water from dyestuff；Absorption method has that equipment investment is relatively fewer with floor space, the simple to operate and excellent feature of decolorizing effect.
In absorption method, conventional adsorbent is mainly activated carbon and ion exchange resin.Activated carbon is as a kind of excellent adsorbent
Early it is widely used in water process, remain the best adsorbent of colored dyes waste water so far, yet with expensive, because
This is typically only applied to the relatively low dye wastewater treatment of concentration；Ion exchange resin has stronger energy of adsorption to dye molecule
Power, but lead to cost for wastewater treatment higher because regeneration is difficult, so limit its popularization in dye wastewater treatment should
With therefore developing a kind of excellent, the cheap adsorbent of absorption property and being always dyestuff and printing and dyeing industrial waste water process
The hot subject of research field.
Montmorillonite also known as montmorillonite, montmorillonite, are a kind of natural minerals of silicate, are the main mine of bentonite ore
Thing component, its composition is mainly sio2And al2o3.Montmorillonite has the characteristics that rich reserves and cheap, its significant property
It is ion-exchange capacity and absorption property, is to replace one of optimal material of activated carbon in industrial adsorbents, can be used to decontaminate
Some pollutants in water.But because montmorillonite surface is negatively charged, therefore it is directly used in dye wastewater treatment adsorption effect non-
Constant is it is difficult to remove the anionic pollutant in waste water.Therefore montmorillonite must be modified processing, can be only achieved for contaminating
The purpose of material wastewater treatment.
The purpose of the present invention is exactly to develop a kind of to have stronger adsorption bleaching energy to dyestuff in dyestuff and printing and dyeing industrial waste water
Cationic polymer modified montmorillonoid adsorbent of power and preparation method thereof.
Content of the invention
A kind of cationic polymer modified montmorillonoid adsorbent is it is characterised in that prepare as follows: in mass concentration
For, in 90% alcoholic solution, while being slowly added dropwise amino silicane coupling agent, while adjusting ph=3-4 with acetic acid, after dripping off, continuing stirring extremely molten
Liquid is transparent, obtains the amino silicane coupling agent solution for standby that mass fraction is 0.1%-3%；The amino silane weighing above-mentioned preparation is coupled
Agent solution, adds montmorillonite, after 30-60 minute is stirred at room temperature, filters, after filter cake is dried 1-3 hour at 50-60 DEG C, then 120
DEG C freeze-day with constant temperature reaction 1-2 hour, cooling, obtain aminosilane coupling agent modifying montmorillonite standby；The amino silane of preparation is even
After connection agent modified montmorillonoid is mixed with polyepichlorohydrin-dimethylamine cationic polymer solution more dry at 50-60 DEG C
Dry, to constant weight, take out material, pulverize, obtain cation-modified montmorillonite sorbent；Alcohol solution described above is that methyl alcohol is molten
Liquid, or ethanol solution；Silane coupler described above is 3- aminopropane triethoxysilane, or 3- aminopropane trimethoxy
Base silane, or 3- aminopropane-methyldiethoxysilane；Montmorillonite described above is calcium-base montmorillonite, or sodium Ji Mengtuo
Soil, its cation exchange capacity 50-100mmol/100g；Polyepichlorohydrin-dimethylamine cationic polymer described above
Solution, the exposed terminated groupses of its cationic polymer are epoxide group, and solution ph is more than 9.
The cationic polymer modified montmorillonoid adsorbent one side of present invention preparation can be substantially improved montmorillonite to dye
Material and Dye Adsorption decoloring ability in printing and dyeing industrial waste water, the especially adsorption capacity to anionic dyes, simultaneously acceptable
Overcome prior art exist cationic polymer be combined with montmorillonite loosely, decolorization cationic polymer be easy to from
The shortcoming that montmorillonite departs from, with the cationic polymer modified montmorillonoid adsorbent of present invention preparation, using absorption method to dyestuff
Processed with printing and dyeing industrial waste water, compared with strong-base anion-exchange resin, can substantially be reduced operating cost.
Further illustrate the present invention below by instantiation.
Specific embodiment
Embodiment 1
The preparation of polyepichlorohydrin-dimethylamine cationic polymer solution: by document (yellow new photograph etc., cationic polymer
Preparation and application performance, chemical industry and engineering, 2009,26 (2), p114-118) synthetically prepared Hydrin-diformazan
Amine cation polymer solution, wherein monomer epoxychloropropane are 1.5:1 with the mol ratio of monomer dimethylamine, crosslinking agent divinyl
Triamine consumption accounts for the 2% of monomer epoxychloropropane and dimethylamine gross mass.Prepared polyepichlorohydrin-dimethylamine cation
Polymer solution, solid content is 33.33%, and outward appearance is weak yellow liquid, and viscosity is 300-500mpa s, and ph is 4-5.
Embodiment 2
The preparation of silane coupler modified montmorillonite: weigh the ethanol that 190 gram mass concentration are 90%, adjust ph=3-3.5 with acetic acid,
It is slowly added dropwise 2 grams of silane coupler 3- aminopropane triethoxysilanes under ph=3-3.5, after dripping off, continue stirring 30-60
Minute transparent to solution, add the ethanol that mass concentration is 90%, to 200 grams of total amount, obtain the amino silane that mass fraction is 1% even
Connection agent solution is standby；100 grams of amino silicane coupling agent solution weighing above-mentioned preparation is put in 250ml beaker, adds 40 grams
Montmorillonite, after being stirred at room temperature 30 minutes, filters, after filter cake is vacuum dried 2 hours at 50 DEG C, then at 120 DEG C of normal pressure freeze-day with constant temperature
Reaction 1 hour, cooling, obtain silane coupler modified montmorillonite.
Embodiment 3
The preparation of cation-modified montmorillonite sorbent a: weigh 40g embodiment 1 preparation polyepichlorohydrin-dimethylamine sun from
Sub- polymer solution (solid content is 33.33%) is mixed with 260g water, adds 10g NaOH, after being uniformly mixed.Again
Add 190g montmorillonite while stirring, after stirring, put in vacuum drying chamber, in 50 DEG C of drying under reduced pressure, to constant weight, powder
Broken, obtain cation-modified montmorillonite sorbent a.
Embodiment 4
The preparation of cation-modified montmorillonite sorbent b: with embodiment 3, simply 190g montmorillonite is changed to prepared by embodiment 2
Silane coupler modified montmorillonite, obtains cation-modified montmorillonite sorbent b.
Embodiment 5
Adsorption bleaching characteristic is tested: is changed with 20g montmorillonite, 20g cation-modified montmorillonite sorbent a and 20g cation respectively
Property montmorillonite sorbent b be adsorbent, using dry column-packing, prepare the thin layer chromatography post of a diameter of 20mm, at room temperature to mould
Intend waste water from dyestuff (500 mg/l) and carry out column chromatography, record colourless chromatography liquid and amass, result is as shown in table 1.
Table 1 adsorbent adsorption bleaching characteristic
The as shown by data of table 1, the cation-modified montmorillonite sorbent a adsorption bleaching characteristic using montmorillonite preparation is significantly larger than
Montmorillonite, and adopt the adsorption bleaching of the cation-modified montmorillonite sorbent b of aminosilane coupling agent modifying montmorillonite preparation
Performance further enhances, and compared with montmorillonite, its decoloring ability is improved significantly.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, the art
Those of ordinary skill, in the essential scope of the present invention, change, interpolation or the replacement made, all should belong to the guarantor of the present invention
Shield scope.
Claims (2)
1. a kind of preparation method of cationic polymer modified montmorillonoid adsorbent is it is characterised in that implement as follows:
Mass concentration is in 90% alcohol solution, while being slowly added dropwise amino silicane coupling agent, while adjusting ph=3-4 with acetic acid, after dripping off, continues
Continuous stirring is transparent to solution, obtains the amino silicane coupling agent solution for standby that mass concentration is 0.1%-3%；Weigh the ammonia of above-mentioned preparation
Base silane coupling agent solution, adds montmorillonite, after 30-60 minute is stirred at room temperature, filters, filter cake is dried 1-3 hour at 50-60 DEG C
Afterwards, react 1-2 hour, cooling then at 120 DEG C of freeze-day with constant temperature, obtain aminosilane coupling agent modifying montmorillonite standby；By preparation
After aminosilane coupling agent modifying montmorillonite is mixed with polyepichlorohydrin-dimethylamine cationic polymer solution, in 50-
It is dried at 60 DEG C, to constant weight, take out material, pulverize, obtain cation-modified montmorillonite sorbent；Alcohol solution described above is
Methanol solution, or ethanol solution；Silane coupler described above is 3- aminopropane triethoxysilane, or 3- aminopropane
Trimethoxy silane, or 3- aminopropane-methyldiethoxysilane；Montmorillonite described above is calcium-base montmorillonite, or sodium
Base montmorillonite, its cation exchange capacity is 50-100mmol/100g；Polyepichlorohydrin-dimethylamine sun described above from
Sub- polymer solution, the exposed terminated groupses of its cationic polymer are epoxide group, and solution ph is more than 9.
2. a kind of cationic polymer modified montmorillonoid adsorbent is it is characterised in that according to preparation method system described in claim 1
Standby and obtain.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107456956A (en) * | 2017-07-26 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyester macromolecule/clay composite adsorbing material preparation method and products thereof and application |
| CN108914245A (en) * | 2018-07-13 | 2018-11-30 | 安徽智博新材料科技有限公司 | A kind of mask filter disc of high-efficient purification air and preparation method thereof |
| CN109181760A (en) * | 2018-10-30 | 2019-01-11 | 安徽海德化工科技有限公司 | A kind of production method of aromatic naphtha |
| CN109518530A (en) * | 2018-11-02 | 2019-03-26 | 杭州特种纸业有限公司 | Thick vulcan fibre of a kind of lamination and preparation method thereof |
| CN111470576A (en) * | 2020-04-10 | 2020-07-31 | 华东理工大学 | Application of porous cationic polymer in removal of dye or heavy metal in wastewater |
| WO2022095360A1 (en) * | 2020-11-05 | 2022-05-12 | 金发科技股份有限公司 | Self-assembled network polyamide composition and preparation method therefor and application thereof |
| CN115301213A (en) * | 2022-08-08 | 2022-11-08 | 江苏索普化工股份有限公司 | Polyaniline/montmorillonite/charcoal composite adsorption material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107456956A (en) * | 2017-07-26 | 2017-12-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyester macromolecule/clay composite adsorbing material preparation method and products thereof and application |
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| CN108914245A (en) * | 2018-07-13 | 2018-11-30 | 安徽智博新材料科技有限公司 | A kind of mask filter disc of high-efficient purification air and preparation method thereof |
| CN109181760A (en) * | 2018-10-30 | 2019-01-11 | 安徽海德化工科技有限公司 | A kind of production method of aromatic naphtha |
| CN109518530A (en) * | 2018-11-02 | 2019-03-26 | 杭州特种纸业有限公司 | Thick vulcan fibre of a kind of lamination and preparation method thereof |
| CN111470576A (en) * | 2020-04-10 | 2020-07-31 | 华东理工大学 | Application of porous cationic polymer in removal of dye or heavy metal in wastewater |
| WO2022095360A1 (en) * | 2020-11-05 | 2022-05-12 | 金发科技股份有限公司 | Self-assembled network polyamide composition and preparation method therefor and application thereof |
| CN115301213A (en) * | 2022-08-08 | 2022-11-08 | 江苏索普化工股份有限公司 | Polyaniline/montmorillonite/charcoal composite adsorption material and preparation method and application thereof |
| CN115301213B (en) * | 2022-08-08 | 2023-10-13 | 江苏索普化工股份有限公司 | Polyaniline/montmorillonite/charcoal composite adsorption material and preparation method and application thereof |
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