CN104971694B - A kind of Inorganic whisker bentonite clay material and its preparation method and application - Google Patents
A kind of Inorganic whisker bentonite clay material and its preparation method and application Download PDFInfo
- Publication number
- CN104971694B CN104971694B CN201510415644.1A CN201510415644A CN104971694B CN 104971694 B CN104971694 B CN 104971694B CN 201510415644 A CN201510415644 A CN 201510415644A CN 104971694 B CN104971694 B CN 104971694B
- Authority
- CN
- China
- Prior art keywords
- bentonite
- inorganic
- aluminium
- pillared
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a kind of Inorganic whisker bentonite clay material and its preparation method and application.The Inorganic whisker bentonite clay material through the following steps that prepare：It is 1 by mass ratio:0.1 0.5 aluminium pillared bentonite reacts 38 hours with chitosan quaternary ammonium salt at 50 90 DEG C, and chitosan quaternary ammonium salt aluminium pillared bentonite is obtained.It increased bentonitic specific surface area, pore volume and heat endurance by inorganic modified, while by the further organically-modified adsorption capacity for making it have organic carbon content higher, increased to organic matter.The Inorganic whisker bentonite clay material that the present invention is provided can be used for water process, be a kind of novel environment friendly bentonite clay material of non-secondary pollution the characteristics of it has efficient, safe.
Description
Technical field
The invention belongs to bentonite processed and applied field, and in particular to a kind of inorganic-organic bentonites material and its
Preparation method and application.
Background technology
Bentonite (bentonite), also known as swelling rock or bentonite, is the claystone-illiteracy with montmorillonite as main component
De- stone claystone, bentonite that China occurs also known as bentonite, as soil, bentonite, amargosite etc..
Bentonite structure cell particle is tiny, with very big specific surface area, in addition with many excellent physicochemical properties,
Including cohesiveness, adsorptivity, catalysis activity, thixotropy, plasticity, lubricity and cation exchange etc..Swelling soil structure
Interlamination region, is mainly filled by the inorganic hydrated cation of interchangeability and hydrone, and the regulation and control of its structure and properties are in recent years
Study hotspot.By ion exchange, the method such as pillared is crosslinked, bentonitic interlamellar spacing, interlamination region electric charge and dielectric ring can be changed
Border, prepares the functional material of various different purposes.
With inorganic ions, especially poly hydroxy metal cation, exchangeable cation between substitution bentonite bed and insert
Entering structure sheaf can prepare inorganic pillared bentonite.Research to pillared bentonite at present relates generally to Al, Fe, Cr, Zr etc.
Single poly hydroxy metal cation or hybrid metal polymer, by document (J.L.Valverde et.al,
Synthesis and characterization of PILCs with single and mixed oxide pillars
prepared from two different bentonites.A comparative study,Microporous and
Mesoporous Materials,1999,267:281) it can be found that the pillared bentonitic effect of hydroxy Al ion is preferable.
From Smith organoammonium ions (R-NH3 +) synthesize organobentonite first since, have many this sides both at home and abroad
The research in face, design has synthesized a series of organobentonites.Organobentonite is to nonpolar or low pole organic pollution suction
Attached effect is substantially better than inorganic bentonite, and the reagent type currently used for Organic Modification of Bentonites is more, and such as coupling agent, surface are lived
Property agent, organic acid, organic amine etc., but most study or surfactant.It is organic with surfactant-modified bentonite
Carbon content is high, the characteristic with hydrophobic oleophilic oil, hence it is evident that enhance the adsorption capacity to Organic substance in water.
But contaminant component is complicated in actual waste water, to improve to inorganic in actual waste water, organic pollution energy of adsorption
Power can prepare inorganic-organic hybrid modified alta-mud to increase bentonitic versatility.It is required that composite bentonite not only has
The larger specific surface area of inorganic bentonite and heat endurance higher, also with organobentonite organic carbon content it is high the characteristics of.
Conventional inorganic-organic hybrid modified alta-mud is general using poly hydroxy metal cation as inorganic modifier at present, with table
Face activating agent is used as organic modifiers, such as Zhu Lizhong (Simultaneous sorption of phosphate and
phenanthrene to inorgano-organo-bentonite from water,Journal of Hazardous
Materials,2006,136(3):982-988) utilize the montmorillonite that is polymerized with cetyl trimethylammonium bromide to swelling
Soil carries out composite modified, and the adsorbent of preparation has adsorption rate higher to phosphate and phenanthrene.But due to organic modifiers and swelling
The active force of soil is weaker, and surfactant is easy to fall off during water pollutant is adsorbed, it is more difficult to biodegradable, thus deposits
In secondary pollution.In order to adapt to highly efficient, safe environmental protection concept, the inorganic-organic for being badly in need of exploring non-secondary pollution is answered
Close modified alta-mud.
The content of the invention
To solve the above problems, it is an object of the invention to provide a kind of preparation of inorganic-organic bentonites material
Method, material non-secondary pollution obtained in the method can be used as a kind of environment-friendly type adsorbent.
It is a further object of the present invention to provide the inorganic-organic bentonites material as obtained in the above method.
It is yet another object of the invention to provide application of the above-mentioned inorganic-organic bentonites material in terms of water process.
To reach above-mentioned purpose, the invention provides a kind of preparation method of inorganic-organic bentonites material, the party
Method is comprised the following steps：
It is 1 by mass ratio:It is small that the aluminium pillared bentonite of 0.1-0.5 reacts at 50-90 DEG C 3-8 with chitosan quaternary ammonium salt
When, chitosan quaternary ammonium salt-aluminium pillared bentonite, i.e., described inorganic-organic bentonites material is obtained.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the method also includes：Described
After reaction 3-8 hours, the reaction solution to obtaining carries out the step of suction filtration, drying.
Shitosan is by β (1,4) -2- amino -2- deoxidation-D- glucans and β (1,4) -2- acetylaminohydroxyphenylarsonic acid 2- deoxidations-D-
The linear natural polymer copolymer that glucan is constituted, is unique polysaccharide that largely there is basic amine group, source in natural carbohydrate
Extensively, it is the product of chitin deacetylase base generation, and chitin is the second largest day that content is only second to cellulose in nature
Right macromolecular compound.Shitosan has many excellent characteristics, such as bactericidal, good adsorptivity, biological degradability
With biocompatibility etc..Shitosan has excellent flocculation ability, but because its is relatively costly, industrial shitosan application at present
Being mainly in water treatment field, shitosan is used for the treatment of food processing wastewater as high polymer coagulant.By by shitosan
Cheap adsorbent this with bentonite is used in combination, and can substantially reduce cost, is provided to be applied to water treatment field
A kind of possibility.But this macromolecular compound of shitosan is not easily accessible bentonitic interlayer due to its larger molecular structure,
If any document report (chitin modified bentonite and its to Pb in water2+Absorption property, Mineral Engineering research, 2012,27 (1)：
68-74) chitin modified bentonite has similar XRD to bentonite original soil, and interlamellar spacing does not change, and this is just
Illustrate that shitosan is not intercalation into bentonite, simply adsorb on bentonitic surface.
The method that the present invention is provided first increases bentonitic interlamellar spacing using the pillared liquid of aluminium, then becomes chitosan quaternary ammoniumization
Into quaternary ammonium salt, finally, between chitosan quaternary ammonium salt is inserted bentonite bed by reaction, inorganic-organic bentonites material is obtained
Material.The material not only has larger specific surface area and pore volume, good heat endurance and the adsorption capacity to organic matter, and
And compared with existing inorganic-organic bentonites material, shitosan is difficult for drop-off, and shitosan is degradable as one kind
Biomaterial, even if coming off also environment will not be polluted.
Hydroxy aluminum ion has many excellent characteristics as a kind of conventional inorganic column-supporting agent, may be inserted into swelling
The larger inorganic bentonite of specific surface area, interlamellar spacing is prepared between soil layer.But shitosan is water insoluble, if being dissolved in some
Mixing with inorganic modifier again after acid solution can destroy the existence form of hydroxy aluminum ion；And enter swollen in directly load
In the case of between profit soil layer, its active force is weaker.In the present invention, after shitosan being made into chitosan quaternary ammonium salt, can not only be with
Inorganic modified bentonite is fully contacted reaction in water, and more can readily enter swelling in the form of ion exchange
Between soil layer, meanwhile, shitosan not only maintains the fundamental property of shitosan, and can increase its flocculation energy by quaternized
Power and restraining and sterilizing bacteria (Spinelli VA et.al, Preparation and characterization of
quaternary chitosan salt:adsorption equilibrium of chromium(VI)ion.React
Funct Polym 2004,61:347-352)。
Research most inorganic-organic hybrid modified alta-muds in, typically using poly hydroxy metal cation as
Inorganic modifier, using surfactant as organic modifiers, in modifying process, surfactant is usually and poly hydroxyl
Metal cation is directly mixed together common modified alta-mud；Selection mixes common modified main cause：Through
The pillared bentonite of poly hydroxy metal cation is crossed, its cation exchange capacity can be reduced, and this will be to sequent surface activating agent
Intercalation bring adverse effect.But it be need to considering it is important that the spy of chitosan quaternary ammonium salt in the modified scheme that the present invention is provided
Different structure, because if by chitosan quaternary ammonium salt and the direct mixed and modified bentonite of the pillared liquid of aluminium, can be due to chitosan quaternary ammonium salt
Larger molecular structure and be in a disadvantageous position in the competition of hydroxy aluminum ion；Therefore, the scheme that the present invention is provided is first
Shitosan is carried out it is quaternized, then with reacted through the modified modified alta-mud with larger interlamellar spacing of the pillared liquid of aluminium
The modified method of substep, in the method, when being further modified to aluminium pillared bentonite using chitosan quaternary ammonium salt, due to without polymerization
The aluminum ions competition of hydroxyl, and aluminium pillared bentonite dehydroxylation in heating, these two aspects are all inserted beneficial to chitosan quaternary ammonium salt
Enter bentonitic interlayer.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the aluminium pillared bentonite is with dense
Spend for the form of 1-10% aluminium pillared bentonite suspensions adds (solvent is water)；
The chitosan quaternary ammonium salt is to add in form of an aqueous solutions.
It is further preferred that the consumption of chitosan quaternary ammonium saline solution reclaimed water is that chitosan quaternary ammonium salt can be made to be completely dissolved i.e.
Can.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the aluminium pillared bentonite is swollen
Through inorganic modified obtained, the bentonite is natural sodium bentonite to profit soil, and smectite content is 60-90%.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the aluminium pillared bentonite is swollen
Profit soil is modified obtained through the pillared liquid of the tripolymer of aluminium ten, and modifying process is comprised the following steps：Bentonite is dispersed in water configuration
It is the medicinal bentonite suspension of 1-10% into mass percent concentration, at 50-90 DEG C, in alum clay than the ratio for 6-20mol/Kg
To in the medicinal bentonite suspension add the pillared liquid of tripolymer of aluminium ten, the reaction time is 2-6h, it is aging after through suction filtration, washing, do
Dry, crushing is obtained the tripolymer pillared bentonite of aluminium ten；Alum clay ratio refers to the addition pillared liquid of tripolymer of aluminium ten in every kilogram of bentonite
Mole (mole calculated on the basis of Al in the pillared liquid of the tripolymer of aluminium ten).
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the pillared liquid of the tripolymer of the aluminium ten
Through the following steps that prepare：It is the AlCl of 0.1-1.0mol/L to concentration at 50-90 DEG C3·6H2Added in O solution dense
The NaOH solution for 0.1-1.0mol/L is spent, the consumption of the two is respectively with Al3+And OH-Meter, mol ratio is 1:2.0-2.5, reaction
Aging 12-48h at room temperature after 2-6 hours, obtains the pillared liquid of tripolymer of aluminium ten；It is further preferred that AlCl3·6H2O solution
With the consumption of both NaOH solutions respectively with Al3+And OH-Meter, mol ratio is 1:2.4.
Al3+Hydrolyzed in water, can be with variform product.Wherein morphon has [Al (OH2)6]3+、[Al
(OH)]2+、[Al(OH)2]+There is [(H Deng, oligomer form2O)8Al2(OH)2]4+、[Al3(OH)4]5+、[Al7(OH)17]4+Deng,
Middle high polymer [Al10(OH)22]8+、[AlO4Al12(OH)24(OH2)12] 7+(Keggin ions, the tripolymer of aluminium ten), [Al24
(OH)60]12+Deng.Al3+These ions are all present when being hydrolyzed in water, and simply ions different under different conditions accounts for leading.
In the present invention, by making Al3+Hydrolyzed under above-mentioned specific environment, most tripolymers of aluminium ten can be synthesized, therefore be defined as aluminium
The pillared liquid of ten tripolymers.During liquid modified alta-mud pillared using the tripolymer of aluminium ten, preferably effect can be obtained.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that the chitosan quaternary ammonium salt is logical
Cross following methods preparation：Shitosan is dissolved in the acetic acid aqueous solution that concentration of volume percent is 0.5-5%, hydrogen is subsequently adding
Sodium hydroxide solution separates out shitosan, and obtaining shitosan filter cake through suction filtration (because the loss of shitosan in experiment is smaller, will can be somebody's turn to do
Loss is ignored, therefore the consumption of shitosan is approximately equal to the quality of filter cake)；In general acetic acid can with hydrolyzing chitosan, but
Can not consider because dissolution time is shorter hydrolysis in this experiment, therefore the shitosan for separating out is only equivalent to the shell of water swelling and gathers
Sugar, what is contacted when so with quaternary ammonium reactant salt is more abundant, is also advantageous for quaterisation.
At 50-80 DEG C, calculated with mole, to addition solvent in 1 part of shitosan filter cake and 4-6 parts of glycidol
Trimethyl ammonium chloride, then pH=8-10 is adjusted to sodium hydroxide solution, then proceeding to react 10-24h, reaction adds third after terminating
Ketone is precipitated, and the sediment for obtaining is obtained chitosan quaternary ammonium salt through suction filtration, low temperature drying again.It is further preferred that solvent
Volume is 60-100 with the ratio of chitosan mass:1mL/g.
In the preparation method of above-mentioned inorganic-organic bentonites material, shitosan uses hydrogen-oxygen again after acetic acid
Change sodium solution to separate out, the shitosan for obtaining is easier to be reacted with glycidyl trimethylammonium chloride；And the process is also with right
Shitosan purifying effect, it is not necessary to independent purification process is carried out to shitosan again, using when operate easier, production cost more
It is low.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that preparing chitosan quaternary ammonium salt
In, deacetylation >=80% (mole is calculated with glucose monomer) of the shitosan.
In the preparation method of above-mentioned inorganic-organic bentonites material, it is preferable that preparing chitosan quaternary ammonium salt
In, the solvent is one or two the combination in water and isopropanol.
In the preferred embodiment of the present invention, the preparation method bag of the inorganic-organic bentonites material
Include following steps：
It is the AlCl of 0.1-1.0mol/L to concentration at 50-90 DEG C3·6H2It is 0.1- that concentration is added in O solution
The NaOH solution of 1.0mol/L, the consumption of the two is respectively with Al3+And OH-Meter, mol ratio is 1:2.0-2.5 (preferably 1：2.4),
Aging 12-48h at room temperature after reaction 2-6 hours, obtains the pillared liquid of tripolymer of aluminium ten；
Bentonite is dispersed in water the medicinal bentonite suspension for being configured to that concentration is 1-10%, at 50-90 DEG C, by alum clay
Than the ratio for 6-20mol/Kg to the pillared liquid of tripolymer of the aluminium ten is added in the medicinal bentonite suspension, the reaction time is 2-
6h, reaction is obtained the tripolymer pillared bentonite of aluminium ten after terminating through suction filtration, washing, drying, crushing；
Shitosan is dissolved in the acetic acid aqueous solution that concentration is 0.5-5%, being subsequently adding sodium hydroxide solution makes shitosan
Separate out, shitosan filter cake is obtained through suction filtration, at 50-80 DEG C, calculated with mole, added in 1 part of shitosan filter cake
Appropriate solvent and 4-6 parts of glycidyl trimethylammonium chloride, then pH=8-10 is adjusted to sodium hydroxide solution, then proceed to reaction
10-24h, reaction adds acetone to be precipitated after terminating, and the sediment for obtaining is obtained chitosan quaternary ammonium through suction filtration, low temperature drying again
Salt；
The tripolymer pillared bentonite of aluminium ten is dispersed in water and is configured to concentration for the pillared swelling of tripolymer of 1-10% aluminium ten
Native suspension, chitosan quaternary ammonium saline solution is configured to by chitosan quaternary ammonium salt, and the chitosan quaternary ammonium saline solution is added
In the tripolymer pillared bentonite suspension of the aluminium ten, reacted 3-8 hours at 50-90 DEG C, chitosan quaternary ammonium salt-aluminium post is obtained
Support bentonite, the tripolymer pillared bentonite of the aluminium ten is 1 with the mass ratio of the chitosan quaternary ammonium salt:0.1-0.5.
Present invention also offers the inorganic-organic bentonites material as obtained in the above method, the material can be used as one
Plant the environment-friendly type adsorbent of non-secondary pollution.
Invention additionally provides application of the above-mentioned inorganic-organic bentonites material in water process.
In the present invention, bentonite is keeping inorganic pillared bentonite specific surface by inorganic composite modified with organic
There is organobentonite organic carbon content high again on the basis of product is higher with heat endurance.The bentonite ratio being prepared
Surface area, pore volume, interlamellar spacing, stability are preferable, have well adapting to property and versatility to actual waste water.Simultaneously because
The organic modifiers that the bentonite is used are degradable environment-friendly reagent-chitosan quaternary ammonium salt, therefore, what the present invention was provided
Inorganic-organic bentonites material will not introduce secondary pollution when waste water is processed.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Following explanation is carried out to used characterizing part method in the embodiment of the present invention：
(1) X-ray diffraction analysis：
Instrument is Holland's PANalytialX ' Pert Powder type x-ray diffractometers, and (ripple is radiated using Cu-K α
It is a length of), tube current 40mA, tube voltage 40kV, 0.013 °/s of step-length, the scanning angle scope of the material phase analysis used is
1°-10°、1°-70°；
Method of testing：Take appropriate testing sample, with mortar grinder to viscous wall after, at 110 DEG C dry 2 hours；Will be dry
Dry good sample is gently pressed into the thin slice of surfacing, to be measured.
(2) low temperature nitrogen adsorption/desorption：
The pore structure and specific surface area data of sample are obtained using low temperature nitrogen physical absorption detachment assays, instrument is
U.S. MicromeriticsTriSTAR3020 type physical adsorption appearances；
Testing procedure and method are：Testing sample is ground into powder, appropriate drying is taken；In 110 DEG C of vacuum (about
1.33Pa) degassing process 8 hours in atmosphere, being fully contacted therewith with liquid nitrogen under 77K (- 196 DEG C) makes to reach adsorption equilibrium；Root
According to the residual volume after total addition and adsorption equilibrium of nitrogen, the adsorbance of nitrogen is calculated.
(3) adsorption experiment：
The diesel oil aqueous solution of a certain amount of 500ppm is configured, it is adsorbed under the conditions of 25 DEG C of sample, used after separation of solid and liquid
N-hexane extraction, the diesel oil concentration after being adsorbed with ultraviolet-visible scene photometric determination at 220nm to extract；Standard is bent
Line equation is C (mg/L)=130.7204*A-11.6993.
Embodiment 1
The invention provides a kind of inorganic-organic bentonites material, the preparation process of the material is：
(1) it is the AlCl of 0.2mol/L by concentration3·6H2O solution is placed in 80 DEG C of water-baths, in the stirring of 500rpm constant speed
Under the conditions of be added dropwise thereto isometric concentration be 0.48mol/L NaOH solution, after being added dropwise to complete continue stir 4h, afterwards from water
Taken out in bath and stand aging 24h at room temperature, the pillared liquid of tripolymer of aluminium ten is obtained；
(2) bentonite is dispersed in water the medicinal bentonite suspension for being configured to that mass percent concentration is 5%, is stirred at 80 DEG C
Under the conditions of mixing, the ratio in alum clay than 10mol/kg is added dropwise the pillared liquid of tripolymer of aluminium ten thereto；Continue to stir after being added dropwise to complete
4h, after through suction filtration, washing, drying, crushing obtain the tripolymer pillared bentonite of aluminium ten, through nitrogen physisorption desorption instrument determine
Its specific surface area is 214m2/ g, pore volume are 0.1569cm3/ g, and the specific surface area of bentonite original soil is 36.8m2/ g, hole body
Product is 0.09338cm3/ g, in addition thermogravimetric analysis find bentonite through the tripolymer of aluminium ten it is pillared after collapse temperature risen to by 875 DEG C
It it is 890 DEG C, this explanation aluminium pillared bentonite has more preferable heat endurance；
(3) by 1 part of shitosan of (mole) commercially available deacetylation >=80% (with glucose monomer calculate mole, under
It is dissolved in together) in the acetic acid aqueous solution that concentration is 1% (percent by volume), stirring, and after complete dissolution under conditions of stirring
0.1mol/L sodium hydroxide solutions are added dropwise thereto, shitosan is separated out, filter cake is obtained through suction filtration；In 80 DEG C and stirring condition
Under, to 5 parts of (mole) glycidyl trimethylammonium chlorides of addition in 1 part of above-mentioned shitosan filter cake, then it is added thereto to water simultaneously
PH=8-9 is adjusted with appropriate sodium hydroxide solution, 20h is reacted under the conditions of 80 DEG C, through suction filtration, low temperature after solution acetone precipitation
It is dried to obtain chitosan quaternary ammonium salt；
(4) the tripolymer pillared bentonite of 20 weight portion aluminium ten is scattered in distilled water and is configured to concentration for 1% (weight hundred
Point ratio) the tripolymer pillared bentonite suspension of aluminium ten, then 9 weight portion chitosan quaternary ammonium salt samples are dissolved in water, resulting solution
In adding the tripolymer pillared bentonite suspension of above-mentioned aluminium ten.Reactor reacts 7h under the conditions of being placed in 80 DEG C, is done through filtering, low temperature
It is dry to can obtain chitosan quaternary ammonium salt-aluminium pillared bentonite sample.
Through its interlamellar spacing of XRD determiningInstrument measurement result is desorbed seeing as organic matter by nitrogen physisorption
Blocking portion duct declines its specific surface area, specific surface area A=163m2/ g, pore volume V=0.1222cm3/g.Use 0.1g samples
Product are adsorbed to the diesel oil in the diesel oil aqueous solution of 20mL500ppm, after 30min is adsorbed after centrifugation, in measure water
Diesel oil concentration, as a result shows that adsorption rate is 94.2%.The unmodified bentonite original soil measured under same experimental conditions is in water
The adsorption rate of diesel oil is 67.7%, and modified adsorption rate improves 39.1%.
Embodiment 2
The invention provides a kind of inorganic-organic bentonites material, the preparation process of the material is：
(1) the tripolymer pillared bentonite of aluminium ten is prepared by the condition of embodiment 1；
(2) it is 2% (percent by volume) shitosan of 1 part of (mole) commercially available deacetylation >=80% to be dissolved in into concentration
In acetic acid aqueous solution, stirring, and 0.1mol/L sodium hydroxide solutions are added dropwise thereto under conditions of stirring after complete dissolution,
Shitosan is separated out, filter cake is obtained through suction filtration；Under 70 DEG C and stirring condition, to 5 parts of addition in 1 part of above-mentioned filter cake shitosan
(mole) glycidyl trimethylammonium chloride, then be added thereto to water and adjust pH=8-9 with appropriate sodium hydroxide solution, in
16h is reacted under the conditions of 70 DEG C, chitosan quaternary ammonium salt is obtained through suction filtration, low temperature drying after solution acetone precipitation；
(3) the tripolymer pillared bentonite of 20 weight portion aluminium ten is scattered in distilled water and is configured to concentration for 5% (weight hundred
Point ratio) the tripolymer pillared bentonite suspension of aluminium ten, then 3 weight portion chitosan quaternary ammonium salt samples are dissolved in water, resulting solution
In adding the tripolymer pillared bentonite suspension of above-mentioned aluminium ten；Reactor reacts 5h under the conditions of being placed in 70 DEG C, is done through filtering, low temperature
It is dry to can obtain chitosan quaternary ammonium salt-aluminium pillared bentonite sample.
Through its interlamellar spacing of XRD determiningInstrument measurement result is desorbed seeing as organic matter by nitrogen physisorption
Blocking portion duct is declined slightly its specific surface area, specific surface area A=194m2/ g, pore volume V=0.1276cm3/g.With
0.1g samples are adsorbed to the diesel oil in the diesel oil aqueous solution of 20mL500ppm, after 30min is adsorbed after centrifugation, are surveyed
Determine diesel oil concentration in water, as a result show that adsorption rate is 90.5%.The unmodified bentonite origin measured under same experimental conditions
Soil is 67.7% to the adsorption rate of the diesel oil in the diesel oil aqueous solution, and modified adsorption rate improves 33.7%.
Embodiment 3
The invention provides a kind of inorganic-organic bentonites material, the preparation process of the material is：
(1) it is the AlCl of 0.4mol/L by concentration3·6H2O solution is placed in 80 DEG C of water-baths, in the stirring of 500rpm constant speed
Under the conditions of be added dropwise thereto isometric concentration be 0.96mol/L NaOH solution, after being added dropwise to complete continue stir 5h, afterwards from water
Taken out in bath and stand aging 32h at room temperature, obtain the pillared liquid of tripolymer of aluminium ten；
(2) bentonite is dispersed in water the medicinal bentonite suspension for being configured to that mass percent concentration is 10%, at 80 DEG C
Under stirring condition, the ratio in alum clay than 15mol/kg is added dropwise the pillared liquid of tripolymer of aluminium ten thereto；Continue to stir after being added dropwise to complete
Mix 5h, after through suction filtration, washing, drying, crushing obtain the tripolymer pillared bentonite of aluminium ten, through nitrogen physisorption desorption instrument survey
Fixed its specific surface area is 213m2/g；
(3) shitosan of 1 part of (mole) commercially available deacetylation >=80% is dissolved in concentration for 0.5% (percent by volume)
Acetic acid aqueous solution in, stirring, and it is molten that 0.1mol/L NaOH is added dropwise under conditions of stirring thereto after complete dissolution
Liquid, separates out shitosan, and filter cake is obtained through suction filtration.Under 60 DEG C and stirring condition, to adding 5 in 1 part of above-mentioned filter cake shitosan
Part (mole) glycidyl trimethylammonium chloride, then be added thereto to water and adjust pH=8-9 with appropriate sodium hydroxide solution, in
15h is reacted under the conditions of 60 DEG C, after solution acetone precipitation, chitosan quaternary ammonium salt is obtained through suction filtration, low temperature drying；
(4) the tripolymer pillared bentonite of 20 weight portion aluminium ten is scattered in distilled water and is configured to concentration for 5% (weight hundred
Point ratio) the tripolymer pillared bentonite suspension of aluminium ten, then 2 weight portion chitosan quaternary ammonium salt samples are dissolved in water, resulting solution
In adding above-mentioned bentonite.Reactor reacts 4h under the conditions of being placed in 60 DEG C, is that can obtain chitosan quaternary ammonium through filtering, low temperature drying
Salt-aluminium pillared bentonite sample.
Through its interlamellar spacing of XRD determiningInstrument measurement result is desorbed seeing as organic matter by nitrogen physisorption
Blocking portion duct is declined slightly its specific surface area, specific surface area A=191m2/ g, pore volume V=0.1348cm3/g.With
0.1g samples are adsorbed to the diesel oil in the diesel oil aqueous solution of 20mL500ppm, after 30min is adsorbed, are centrifuged determining
Diesel oil concentration in water.Result shows that adsorption rate is 89.7%.The unmodified bentonite original soil pair measured under same experimental conditions
The adsorption rate of diesel oil is 67.7% in water, and modified adsorption rate improves 32.5%.
Embodiment 4
The invention provides a kind of inorganic-organic bentonites material, the preparation process of the material is：
(1) the pillared liquid of tripolymer of aluminium ten is prepared by the condition of embodiment 1；
(2) bentonite is dispersed in water the medicinal bentonite suspension for being configured to that mass percent concentration is 10%, at 70 DEG C
Under stirring condition, the pillared liquid of tripolymer of aluminium ten is added dropwise thereto；After being added dropwise to complete continue stir 3h, after through suction filtration, washing, do
Dry, crushing obtains the tripolymer pillared bentonite of aluminium ten；
(3) it is 1% (percent by volume) shitosan of 1 part of (mole) commercially available deacetylation >=80% to be dissolved in into concentration
In acetic acid aqueous solution, stirring is added dropwise sodium hydroxide solution thereto under conditions of stirring after being completely dissolved, analyse shitosan
Go out, filter cake is obtained through suction filtration.Under 80 DEG C and stirring condition, shunk to 6 parts (moles) are added in 1 part of above-mentioned filter cake shitosan
Glycerine trimethyl ammonium chloride, then be added thereto to suitable quantity of water and adjust pH=8-9 with sodium hydroxide solution, it is anti-under the conditions of 80 DEG C
15h is answered, chitosan quaternary ammonium salt is obtained through suction filtration, low temperature drying after solution acetone precipitation.
(4) the tripolymer pillared bentonite of 20 weight portion aluminium ten is scattered in distilled water and is configured to concentration for 5% (weight hundred
Point ratio) suspension；5 weight portion chitosan quaternary ammonium salt samples are dissolved in water, resulting solution is added in above-mentioned bentonite.Reactor
5h is reacted under the conditions of being placed in 80 DEG C, is that can obtain chitosan quaternary ammonium salt-aluminium pillared bentonite sample through filtering, low temperature drying.
Through its interlamellar spacing of XRD determiningInstrument measurement result is desorbed seeing as organic matter by nitrogen physisorption
Blocking portion duct is declined slightly its specific surface area, specific surface area A=177m2/ g, pore volume V=0.1226cm3/g.With
0.1g samples are adsorbed to the diesel oil in the diesel oil aqueous solution of 20mL500ppm, after absorption 30min, are centrifuged determining water
Middle diesel oil concentration, as a result shows that adsorption rate is 91.9%.The unmodified bentonite original soil measured under same experimental conditions is to water
The adsorption rate of middle diesel oil is 67.7%, and modified adsorption rate improves 35.7%.
Embodiment 5
The bentonite clay material being directly modified through chitosan quaternary ammonium salt is present embodiments provided, the preparation process of the material is：
(1) chitosan quaternary ammonium salt is synthesized by the method for step (4) in embodiment 4；
(2) 20 parts by weight of bentonite are scattered in distilled water the suspension for being configured to that mass fraction is 5%；By 5 weight
Part chitosan quaternary ammonium salt sample is dissolved in water, and resulting solution is added in above-mentioned bentonite；In continuing to react 5h under 70 DEG C of water-baths, afterwards
Modified alta-mud is obtained through suction filtration, washing, drying, crushing.
Modified alta-mud obtained in the present embodiment is tested, its specific surface area is determined through nitrogen physisorption desorption instrument
It is 29.6m2/ g, and the specific surface area of non-modified bentonite original soil is 36.8m2/ g, this is because chitosan quaternary ammonium salt adds
Enter so that bentonite content reduces what is caused.
By the XRD diffraction patterns for contrasting modified alta-mud obtained in the present embodiment and bentonite original soil：Both spreads out
Penetrate peak similar, interlamellar spacing is each aboutThe chitosan quaternary ammonium salt of this explanation macromolecular is not inserted into bentonitic
Interlayer.
Embodiment 6
A kind of modified alta-mud is present embodiments provided, it uses chitosan quaternary ammonium salt direct with the pillared liquid of tripolymer of aluminium ten
Mixed and modified bentonitic method, specific preparation process is：
(1) the pillared liquid of tripolymer of aluminium ten is synthesized by the method for step (1) in embodiment 1；
(2) aluminium chitosan quaternary ammonium salt is synthesized by the method for step (4) in embodiment 4：
(3) 20 parts by weight of bentonite are scattered in distilled water the suspension for being configured to that mass fraction is 5%；By 5 weight
Part chitosan quaternary ammonium salt sample is dissolved in water, and resulting solution is added in above-mentioned bentonite, while the ratio in alum clay than 10mol/kg
Thereto plus the pillared liquid of the tripolymer of aluminium ten；In under 70 DEG C of water-baths continue react 5h, after through suction filtration, washing, drying, crush obtain
Modified alta-mud.
Modified alta-mud obtained in the present embodiment is tested, through its interlamellar spacing of XRD determiningThrough nitrogen thing
Reason adsorption/desorption instrument determines its specific surface area for 54.8m2/ g, pore volume V=0.07630cm3/g。
Contrast the interlamellar spacing of aluminium pillared bentoniteUnderstand：The pillared liquid of the tripolymer of aluminium ten is same with chitosan quaternary ammonium salt
When modified alta-mud when chitosan quaternary ammonium salt be not inserted into interlayer, and caused because chitosan quaternary ammonium salt is supported on surface plugging hole
Specific surface area is obviously reduced.
Claims (12)
1. a kind of preparation method of inorganic-organic bentonites material, the method is comprised the following steps：
It is 1 by mass ratio:The aluminium pillared bentonite of 0.1-0.5 reacts 3-8 hours with chitosan quaternary ammonium salt at 50-90 DEG C, makes
Obtain chitosan quaternary ammonium salt-aluminium pillared bentonite, i.e., described inorganic-organic bentonites material.
2. the preparation method of inorganic-organic bentonites material as claimed in claim 1, wherein, the pillared swelling of aluminium
Soil is added in the form of aluminium pillared bentonite suspension with mass percent concentration as 1-10%；
The chitosan quaternary ammonium salt is to add in form of an aqueous solutions.
3. the preparation method of inorganic-organic bentonites material as claimed in claim 1, wherein, the pillared swelling of aluminium
Soil is bentonite through inorganic modified obtained, and the bentonite is natural sodium bentonite, and its smectite content is 60-90%.
4. the preparation method of the inorganic-organic bentonites material as described in claim any one of 1-3, wherein, the aluminium
Pillared bentonite is bentonite modified obtained through the pillared liquid of the tripolymer of aluminium ten, and modifying process is comprised the following steps：
Bentonite is dispersed in water the medicinal bentonite suspension for being configured to that mass percent concentration is 1-10%, at 50-90 DEG C,
In alum clay than the ratio for 6-20mol/Kg to the addition pillared liquid of tripolymer of aluminium ten in the medicinal bentonite suspension, the reaction time is
2-6h, reaction is obtained the tripolymer pillared bentonite of aluminium ten after terminating through suction filtration, washing, drying, crushing.
5. the preparation method of inorganic-organic bentonites material as claimed in claim 4, wherein, the tripolymer of the aluminium ten
Pillared liquid through the following steps that prepare：
It is the AlCl of 0.1-1.0mol/L to concentration at 50-90 DEG C3·6H2It is 0.1-1.0mol/L that concentration is added in O solution
NaOH solution, the consumption of the two is respectively with Al3+And OH-Meter, mol ratio is 1:2.0-2.5, after reacting 2-6 hours at room temperature
Aging 12-48h, obtains the pillared liquid of tripolymer of aluminium ten.
6. the preparation method of inorganic-organic bentonites material as claimed in claim 5, wherein, AlCl3·6H2O solution
With the consumption of both NaOH solutions respectively with Al3+And OH-Meter, mol ratio is 1:2.4.
7. the preparation method of inorganic-organic bentonites material as claimed in claim 1, wherein, the chitosan quaternary ammonium
Salt is prepared by the following method：
Shitosan is dissolved in the acetic acid aqueous solution that concentration of volume percent is 0.5-5%, being subsequently adding sodium hydroxide solution makes
Shitosan is separated out, and shitosan filter cake is obtained through suction filtration；
At 50-80 DEG C, calculated with mole, to addition solvent in 1 part of shitosan filter cake and 4-6 parts of glycidol front three
Ammonium chloride, then pH=8-10 is adjusted to sodium hydroxide solution, then proceeding to react 10-24h, reaction adds acetone to enter after terminating
Row precipitation, the sediment for obtaining is obtained chitosan quaternary ammonium salt through suction filtration, low temperature drying again.
8. the preparation method of inorganic-organic bentonites material as claimed in claim 7, wherein, the volume and shell of solvent
The ratio of glycan quality is 60-100:1mL/g.
9. the preparation method of inorganic-organic bentonites material as claimed in claim 7 or 8, wherein, the shitosan
Deacetylation >=80%.
10. the preparation method of inorganic-organic bentonites material as claimed in claim 7 or 8, wherein, the solvent is
One or two combination in water and isopropanol.
Inorganic-organic bentonites material obtained in a kind of 11. methods as described in claim 1-10 any one.
The application of inorganic-organic bentonites material described in 12. claims 11 in water process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510415644.1A CN104971694B (en) | 2015-07-15 | 2015-07-15 | A kind of Inorganic whisker bentonite clay material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510415644.1A CN104971694B (en) | 2015-07-15 | 2015-07-15 | A kind of Inorganic whisker bentonite clay material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104971694A CN104971694A (en) | 2015-10-14 |
| CN104971694B true CN104971694B (en) | 2017-06-27 |
Family
ID=54268986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510415644.1A Active CN104971694B (en) | 2015-07-15 | 2015-07-15 | A kind of Inorganic whisker bentonite clay material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104971694B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348736A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | Modified montmorillonite eco-friendly plastic |
| CN108421537B (en) * | 2016-07-15 | 2019-12-03 | 杭州绿一环保技术有限公司 | A kind of compound adsorbent and its preparation method and application |
| CN106745447A (en) * | 2016-11-25 | 2017-05-31 | 南宁市黑晶信息技术有限公司 | A kind of heavy metal-polluted water process flocculant |
| CN106732425B (en) * | 2016-12-28 | 2019-10-01 | 西北师范大学 | The modified bentonite adsorption material of Quaternary Ammonium Salt of Chitosan and its preparation and the application in Adsorbing Lead Ion in Polluted Water |
| CN106861607A (en) * | 2017-03-17 | 2017-06-20 | 武汉理工大学 | A kind of preparation method of the modified carbon/montmorillonite Composite sorbing material of organic-inorganic |
| CN107282021B (en) * | 2017-08-08 | 2019-09-24 | 中国石油大学(北京) | A kind of Organic-inorganic composite bentonite clay material and its preparation method and application |
| CN108102151B (en) * | 2017-12-14 | 2020-06-19 | 华南理工大学 | Xylan-click-chitosan quaternary ammonium salt/montmorillonite nanocomposite and preparation method thereof |
| CN108970587B (en) * | 2018-06-22 | 2020-06-09 | 西北大学 | Composite modified montmorillonite chitosan cross-linked adsorbent and preparation method thereof |
| CN109279674A (en) * | 2018-09-17 | 2019-01-29 | 深圳市心版图科技有限公司 | A kind of antibacterial and deodouring modified fibre and preparation method thereof for purification of water quality |
| CN109174027A (en) * | 2018-09-19 | 2019-01-11 | 重庆大学 | The preparation method of the fixed aluminium pillared bentonite adsorbent of sodium alginate and its method for adsorbing phosphate radical |
| CN109759030B (en) * | 2019-03-08 | 2021-08-24 | 河北工业大学 | Preparation method of polyacrylic acid composite aluminum modified bentonite water treatment agent capable of adsorbing Cr (VI) |
| CN112316893B (en) * | 2020-10-22 | 2023-07-07 | 华东理工大学 | Preparation method and application of bentonite composite material for adsorbing and degrading site peculiar smell substances |
| CN115536035B (en) * | 2021-06-29 | 2024-05-28 | 中石化南京化工研究院有限公司 | Preparation method of temperature-resistant organic bentonite, temperature-resistant organic bentonite and application thereof |
| CN115231789A (en) * | 2022-08-17 | 2022-10-25 | 东南大学 | Preparation method of printing and dyeing biochemical sludge composite dehydrating agent |
| CN117427618B (en) * | 2023-12-20 | 2024-03-05 | 中国农业大学 | Chitosan modified yellow phosphorus slag-bentonite composite material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0729096B2 (en) * | 1989-06-12 | 1995-04-05 | 荏原インフイルコ株式会社 | Water treatment method |
| CN100434463C (en) * | 2006-09-08 | 2008-11-19 | 武汉大学 | Chitosan quaternary ammonium salt/organic montmorillonite nano composite material and preparation method thereof |
| CN100429146C (en) * | 2006-11-27 | 2008-10-29 | 浙江大学 | Method for synthesizing composite material of organic - inorganic bentonite |
| CN102350300B (en) * | 2011-09-09 | 2013-06-05 | 武汉科技大学 | Enzyme imitation type water treatment agent for degrading polycycic/heterocyclic aromatic hydrocarbon, and preparation method for enzyme imitation type water treatment agent |
-
2015
- 2015-07-15 CN CN201510415644.1A patent/CN104971694B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104971694A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104971694B (en) | A kind of Inorganic whisker bentonite clay material and its preparation method and application | |
| Melo et al. | Cellulose nanowhiskers improve the methylene blue adsorption capacity of chitosan-g-poly (acrylic acid) hydrogel | |
| Peter et al. | Chitin and chitosan based composites for energy and environmental applications: a review | |
| Iftekhar et al. | Synthesis of novel GA-g-PAM/SiO2 nanocomposite for the recovery of rare earth elements (REE) ions from aqueous solution | |
| Heath et al. | Chitin nanowhisker aerogels | |
| CN103861567B (en) | The preparation method of hydroxyapatite/bagasse active carbon | |
| CN109289790B (en) | Preparation method of multifunctional composite hydrogel | |
| CN106517341B (en) | A kind of method and its application for preparing manganese dioxide nano catalyst | |
| Chen et al. | Polyethyleneimine grafted starch nanocrystals as a novel biosorbent for efficient removal of methyl blue dye | |
| CN109364889A (en) | A kind of preparation method and its usage of temperature-sensitive hydrogel | |
| Córdova et al. | Xanthation of alginate for heavy metal ions removal. Characterization of xanthate-modified alginates and its metal derivatives | |
| Mittal et al. | Advances in the role of natural gums-based hydrogels in water purification, desalination and atmospheric-water harvesting | |
| WO2018122878A1 (en) | Method for preparing cellulose microstructures-templated nanocomposites with enhanced arsenic removal capacity and a purifier thereof | |
| Meng et al. | One-pot synthesis of N, N-bis [2-methylbutyl] imidazolium hexafluorophosphate–TiO2 nanocomposites and application for protein isolation | |
| CN107282021A (en) | A kind of organo-mineral complexing bentonite clay material and its preparation method and application | |
| WO2010128204A1 (en) | Novel inorgano-bioorganic nanocomposite materials, their preparation and use | |
| Cen et al. | Covalently-bonded quaternized activated carbon for selective removal of NO3–in capacitive deionization | |
| Zheng et al. | One-step fabrication of imprinted mesoporous cellulose nanocrystals films for selective separation and recovery of Nd (III) | |
| Li et al. | Preparation of green magnetic hydrogel from cellulose nanofibril (CNF) originated from soybean residue for effective and rapid removal of copper ions from waste water | |
| CN108658193A (en) | A kind of preparation method of novel magnetic flocculant | |
| Zhan et al. | Flexible fabrication chitosan-polyamidoamine aerogels by one-step method for efficient adsorption and separation of anionic dyes | |
| AU2021107526A4 (en) | The preparation method and application of malic acid-chitosan nanoporous hydrogel microspheres | |
| CN107413314B (en) | Method for removing chromium in wastewater | |
| Theng | Polysaccharides | |
| CN107200787B (en) | A kind of imidazoles alginate ionic liquid and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |