CN107159098A - A kind of method for preparing modified bentonite - Google Patents
A kind of method for preparing modified bentonite Download PDFInfo
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- CN107159098A CN107159098A CN201710254734.6A CN201710254734A CN107159098A CN 107159098 A CN107159098 A CN 107159098A CN 201710254734 A CN201710254734 A CN 201710254734A CN 107159098 A CN107159098 A CN 107159098A
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- 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
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a kind of method for preparing modified bentonite, bentonite is purified with sodium hexametaphosphate solution, obtains purifying bentonite；In the aluminum saline solution that sodium hydrate aqueous solution is added dropwise to 70~90 DEG C, the first constant temperature aging of temperature-resistant progress is then maintained, hydroxyl-aluminum pillared agent is obtained；Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 70~90 DEG C, molysite aqueous solution is added dropwise in the hydroxyl-aluminum pillared agent, the second constant temperature aging of temperature-resistant progress is then maintained, obtains composite pillared dose of hydroxyl Fe Al；The 3rd constant temperature aging is carried out after the purifying bentonite is mixed with composite pillared dose of the hydroxyl Fe Al, modified alta-mud is obtained.Bentonite is improved to Cd using method for preparing modified bentonite provided by the present invention2+Adsorptivity, while also improving bentonite to Cu2+And Pb2+Adsorptivity.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of method for preparing modified bentonite.
Background technology
Bentonite is a kind of clay minerals being distributed widely in nature, belongs to nonmetallic minerals, and bentonite is usual
It is accompanied with many mineral, its main component is montmorillonite.Montmorillonite belongs to 2:1 structure is i.e. by two layers of silicon-oxy tetrahedron and one
Layer is sandwiched in the monoclinic system silicate mineral that aluminium (magnesium) oxygen (hydrogen-oxygen) octahedron is constituted.Intracell non-equivalence class matter in montmorillonite
(silicon is replaced by Al, Fe in tetrahedron for isomorphous replacement；Aluminium enters line replacement by Fe, Mg plasma in octahedron), make its structure type
Become more complicated, and interlayer structure increase negative electrical charge formation interlayer negative electrical charge, force Liquidity limit to compensate, to reach layer
Between charge balance, with cation exchange property；Additionally, due to bentonite have big, preferable absorption property of specific surface area etc. its
His characteristic, makes bentonite have larger ion exchange capacity.Because bentonite has above-mentioned excellent properties and is widely used in
Field of environment protection, the application in the application (such as landfill impervious material), wastewater treatment such as in waste disposal is (such as weight
Metallic wastewater, organic wastewater and waste water from dyestuff) and otherwise application.
In order to obtain the bentonite of superior performance, bentonite can be modified by the method for physics and chemistry, with
Change its structure and surface characteristic, adapt it to different use requirements.In the prior art, alta-mud modification method mainly has
Activation method is modified, ion-exchange is modified and pillared modification, and wherein pillared modification is the sight for entering into people 1970s
And the technology gradually grown up.Because pillared modified montmorillonite has unique structure and performance, obtain pillared modification
To extensive attention.Column-supporting agent used in pillared modification be divided into organic-pillared dose, inorganic column-supporting agent and mixing column-supporting agent, numerous
In column-supporting agent, hydroxy metal cation column-supporting agent is optimal column-supporting agent.At present, generally by being added dropwise into metal salt solution
Alkali lye, then obtains hydroxy metal cation column-supporting agent through aged at room temperature, but the hydroxy metal for using conventional method to prepare is positive
Ion column-supporting agent modified alta-mud, still can not effectively improve bentonite to Cd2+Adsorptivity.
The content of the invention
It is an object of the invention to provide a kind of method for preparing modified bentonite, modified alta-mud provided by the present invention
Preparation method it is simple to operate, it is possible to increase bentonite is to Cd2+Adsorptivity, while bentonite can also be improved to Cu2+And Pb2+
Adsorptivity.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
A kind of method for preparing modified bentonite, comprises the following steps：
(1) bentonite is purified with sodium hexametaphosphate solution, obtains purifying bentonite；
(2) sodium hydrate aqueous solution is added dropwise in 70~90 DEG C of aluminum saline solution, then maintains temperature-resistant progress
First constant temperature aging, obtains hydroxyl-aluminum pillared agent；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 70~90 DEG C, molysite aqueous solution is added dropwise to the hydroxyl
In aluminium column-supporting agent, the second constant temperature aging of temperature-resistant progress is then maintained, composite pillared dose of hydroxyl Fe-Al is obtained；
(3) the 3rd constant temperature aging is carried out after the purifying bentonite is mixed with composite pillared dose of the hydroxyl Fe-Al,
Obtain modified alta-mud；
There is no the restriction of time sequencing between the step (1) and step (2).
It is preferred that, the purification in the step (1) comprises the following steps：
The bentonite is mixed with the sodium hexametaphosphate solution, constant temperature stirs 0.5~1.5h at 50~70 DEG C,
Obtain mixed liquor；
At a temperature of the constant temperature is stirred, the mixed liquor is subjected to stratification, obtained supernatant liquid is dried
It is dry to obtain purifying bentonite.
It is preferred that, the concentration of the sodium hexametaphosphate solution is 0.15~0.35mol/L, and pH value is 6.5~7.5.
It is preferred that, the volume ratio of the bentonitic quality and the sodium hexametaphosphate solution is 1g:3~4mL.
It is preferred that, the Al in the aluminum saline solution3+, Fe in the sodium hydroxide and the molysite aqueous solution3+Rub
You are than being 1:1.7~2.2:0.05~0.15.
It is preferred that, in the step (2), molysite aqueous solution is added dropwise in the hydroxyl-aluminum pillared agent, the hydroxyl is maintained
The temperature of base aluminium column-supporting agent, constant temperature stirs 2.5~4h, then carries out the second constant temperature aging.
It is preferred that, the time of the first constant temperature aging and the second constant temperature aging independently is 20~30h in the step (2).
It is preferred that, in the step (3), in composite pillared dose of hydroxyl Fe-Al the amount of the total material of metal ion with it is described
Bentonitic mass ratio is purified for 1.0~1.5mmol:1g.
It is preferred that, the step (3) specifically includes following steps：
The purifying bentonite is mixed with water, obtains purifying bentonite suspension；
Under conditions of the temperature of the purifying bentonite suspension is 50~90 DEG C, the hydroxyl that the step (2) is obtained
Composite pillared dose of base Fe-Al is added dropwise in the purifying bentonite suspension, then maintains the purifying bentonite suspension
Temperature, constant temperature stirs 2.5~4.0h, then carries out the 3rd constant temperature aging；
The feed liquid that the 3rd constant temperature aging is obtained obtains modified alta-mud through separation of solid and liquid, washing, drying.
It is preferred that, the temperature of the 3rd constant temperature aging is 50~90 DEG C in the step (3), the 3rd constant temperature aging
Time is 12~36h.
The invention provides a kind of method for preparing modified bentonite, bentonite is carried with sodium hexametaphosphate solution
It is pure, obtain purifying bentonite；In the aluminum saline solution that sodium hydrate aqueous solution is added dropwise to 70~90 DEG C, then temperature is maintained not
Become and carry out the first constant temperature aging, obtain hydroxyl-aluminum pillared agent；In the condition that the temperature of the hydroxyl-aluminum pillared agent is 70~90 DEG C
Under, molysite aqueous solution is added dropwise in the hydroxyl-aluminum pillared agent, the second constant temperature aging of temperature-resistant progress is then maintained, obtains
Composite pillared dose of hydroxyl Fe-Al；It is permanent that the 3rd is carried out after the purifying bentonite is mixed with composite pillared dose of the hydroxyl Fe-Al
Warm aging, obtains modified alta-mud.Preparation method provided by the present invention is carried out using sodium hexametaphosphate solution to bentonite
Purification, improves the content of montmorillonite, swollen to purifying using composite pillared dose of the hydroxyl Fe-Al that aging is obtained at 70~90 DEG C
Profit soil is modified, and with bentonite ion exchange occurs for composite pillared dose of hydroxyl Fe-Al, and interlamellar spacing is expanded, purification step
And the combination that composite pillared dose of hydroxyl Fe-Al, plays synergy and improves modified alta-mud to Cd2+Absorption property.Experiment
As a result show, bentonite is improved to Cd using method for preparing modified bentonite provided by the present invention2+Adsorptivity, can
Effectively remove the Cd in waste water2+, 0.1g modified alta-muds addition 30mLCd2+When concentration is in 50mg/L nitric acid cadmium solution, Cd2 +Clearance be 80.8%~86.0%；In addition, bentonite can also be improved to Cu according to preparation method provided by the present invention2 +And Pb2+Adsorptivity, use 0.1g modified alta-muds add 30mLCu2+When concentration is in 50mg/L copper-bath, Cu2+
Clearance be 67.0%~75.3%, use 0.05g modified alta-muds add 30mLPb2+Concentration is molten for 50mg/L plumbi nitras
When in liquid, Pb2+Clearance be 79.7%~82.0%.
Brief description of the drawings
The XRD of the gained modified alta-mud of Fig. 1 embodiments 1, the gained modified alta-mud of comparative example 1 and bentonite original soil.
Embodiment
The invention provides a kind of method for preparing modified bentonite, comprise the following steps：
(1) bentonite is purified with sodium hexametaphosphate solution, obtains purifying bentonite；
(2) sodium hydrate aqueous solution is added dropwise in 70~90 DEG C of aluminum saline solution, then maintains temperature-resistant progress
First constant temperature aging, obtains hydroxyl-aluminum pillared agent；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 70~90 DEG C, molysite aqueous solution is added dropwise to the hydroxyl
In aluminium column-supporting agent, the second constant temperature aging of temperature-resistant progress is then maintained, composite pillared dose of hydroxyl Fe-Al is obtained；
(3) the 3rd constant temperature aging is carried out after the purifying bentonite is mixed with composite pillared dose of the hydroxyl Fe-Al,
Obtain modified alta-mud；
There is no the restriction of time sequencing between the step (1) and step (2).
The present invention is purified bentonite with sodium hexametaphosphate solution, obtains purifying bentonite.In the present invention, institute
Bentonitic expansion capacity is stated for 5~10mL/g, glue medium is 5~15mL/g, Absorbance ratio-derivative method is 0.4~0.8mmol/g, and cation
Exchange and hold for 5~15cmol/kg.In the present invention, the bentonitic particle diameter preferably 100~300 mesh, more preferably 150~250
Mesh, most preferably 200 mesh.
In the present invention, the purification preferably includes following steps：
The bentonite is mixed with the sodium hexametaphosphate solution, constant temperature stirs 0.5~1.5h at 50~70 DEG C,
Obtain mixed liquor；
At a temperature of the constant temperature is stirred, the mixed liquor is subjected to stratification, obtained supernatant liquid is dried
It is dry to obtain purifying bentonite.
In the present invention, the concentration of the sodium hexametaphosphate solution preferably 0.15~0.35mol/L, more preferably 0.20~
0.30mol/L.In the present invention, the pH value of the sodium hexametaphosphate solution preferably 6.5~7.5, more preferably 7.0.
In the present invention, it is preferred to which the pH value of the sodium hexametaphosphate solution is adjusted using aqueous sodium carbonate.
The present invention does not have particular/special requirement to the concentration of the aqueous sodium carbonate, the pH value of sodium hexametaphosphate solution can be adjusted to
Suitable value, the concentration of the aqueous sodium carbonate is 2~6wt.% in embodiments of the present invention.
In the present invention, the bentonitic quality and the preferred 1g of volume ratio of the sodium hexametaphosphate solution:3~
4mL, more preferably 1g:3.5~3.8mL.
In the present invention, after the bentonite is mixed with the sodium hexametaphosphate solution, preferably at 60~65 DEG C
Carry out constant temperature stirring.In the present invention, time preferably 0.8~1.2h of the constant temperature stirring.
The present invention does not have particular/special requirement to the time of the stratification, and the solid impurity particle that density can be made larger fills
Divide and be deposited on lower floor, in the present invention, time preferably 1~2h of the stratification.In the present invention, stratification
Afterwards, upper strata is suspension, and lower floor is solid impurity, and the present invention preferably slowly topples over upper suspension, obtains supernatant liquid.
The present invention does not have particular/special requirement to the concrete mode of drying, can remove solvent, obtains the purifying swelling of drying
Native solid, can use drying mode well known to those skilled in the art, such as forced air drying, vacuum drying, microwave drying
Deng using forced air drying in the embodiment of the present invention.In invention, temperature preferably 100~115 DEG C, more preferably 105 of the drying
~110 DEG C.In the present invention, the time of the drying preferably 6~8h.
The present invention preferably crushes the bentonite obtained after drying, then crosses 200 mesh sieves, obtains purifying bentonite.
Sodium hydrate aqueous solution is added dropwise to 70~90 DEG C of aluminium by the present invention when preparing composite pillared dose of hydroxyl Fe-Al
In saline solution, the first constant temperature aging of temperature-resistant progress is then maintained, hydroxyl-aluminum pillared agent is obtained.In the present invention, it is described
Preferably 80~85 DEG C of the temperature of aluminum saline solution.
In the present invention, the concentration of the sodium hydrate aqueous solution preferably 0.08~0.15mol/L, more preferably 0.10~
0.12mol/L。
The present invention does not have particular/special requirement to the species of the aluminium salt, can be any water-soluble aluminium salt, such as aluminium chloride,
Aluminum sulfate or aluminum nitrate, in the present invention, it is preferred to aluminium chloride.In the present invention, the concentration of the aluminum saline solution preferably 0.05
~0.15mol/L, more preferably 0.08~0.10mol/L.
Preferably sodium hydrate aqueous solution is slowly added dropwise into aluminum saline solution by the present invention, to avoid aluminum hydroxide precipitation
Formed.In the present invention, preferably state is kept stirring for during sodium hydroxide being added dropwise into aluminum saline solution.In the present invention
In, the preferred 500-1000r/min of rotating speed of the stirring.In the present invention, the rate of addition of the sodium hydrate aqueous solution is excellent
Select 0.2~0.8mL/s.
In the present invention, the Al in the aluminum saline solution3+With the mol ratio preferably 1 of the sodium hydroxide:1.7~2.2,
More preferably 1:2.0~2.1.In the present invention, time preferably 20~30h, the more preferably 22~27h of the first constant temperature aging,
Most preferably 24~26h.
Obtain after hydroxyl-aluminum pillared agent, the present invention the hydroxyl-aluminum pillared agent temperature be 70~90 DEG C under conditions of,
Molysite aqueous solution is added dropwise in the hydroxyl-aluminum pillared agent, the second constant temperature aging of temperature-resistant progress is then maintained, obtains hydroxyl
Composite pillared dose of base Fe-Al.In the present invention, preferably 80~85 DEG C of the temperature of the hydroxyl-aluminum pillared agent.
The present invention does not have particular/special requirement to the species of molysite, can be any water-soluble molysite, such as iron chloride, nitric acid
Iron, ferric sulfate, in the present invention, it is preferred to iron chloride.In the present invention, the concentration of the molysite aqueous solution preferably 0.05~
0.15mol/L, more preferably 0.08~0.10mol/L.In the present invention, the rate of addition of the molysite aqueous solution preferably 0.2~
0.8mL/s。
In the present invention, the Al in the aluminum saline solution3+With the Fe in the molysite aqueous solution3+Mol ratio it is preferred
1:0.05~0.15, more preferably 1:0.10~0.11.In the present invention, molysite aqueous solution is added dropwise to excellent during hydroxy Al
Choosing is kept stirring for state.In the present invention, the preferred 500-1000r/min of the rotating speed of the stirring.
In the present invention, after molysite aqueous solution is added dropwise in the hydroxyl-aluminum pillared agent, the hydroxy Al is preferably maintained
Temperature-resistant, constant temperature 2.5~4h of stirring of column-supporting agent, then carry out the second constant temperature aging.In the present invention, second constant temperature is old
The time of change preferably 20~30h, most preferably more preferably 22~27h, 24~26h.
Obtain after purifying bentonite and composite pillared dose of hydroxyl Fe-Al, the present invention purifies bentonite and the hydroxyl by described
The 3rd constant temperature aging is carried out after composite pillared dose of mixing of base Fe-Al, modified alta-mud is obtained.In the present invention, the step
(3) in, the amount of the total material of the metal ion in composite pillared dose of hydroxyl Fe-Al and the bentonitic mass ratio of purifying
It is preferred that 1.0~1.5mmol:1g, more preferably 1.1~1.3mmol:1g.
In the present invention, the step (3) is preferably carried out in accordance with the following steps：
The purifying bentonite is mixed with water, obtains purifying bentonite suspension；
Under conditions of the temperature of the purifying bentonite suspension is 50~90 DEG C, the hydroxyl that the step (2) is obtained
Composite pillared dose of base Fe-Al is added dropwise in the purifying bentonite suspension, then maintains the temperature-resistant of suspension, constant temperature is stirred
2.5~4.0h is mixed, then carries out the 3rd constant temperature aging；
The feed liquid that the 3rd constant temperature aging is obtained obtains modified alta-mud through separation of solid and liquid, washing, drying.
In the present invention, concentration preferably 3~12g/L, the more preferably 5~10g/L of the purifying bentonite suspension, optimal
Select 7~8g/L.
In the present invention, rate of addition preferably 1~3mL/min of composite pillared dose of the hydroxyl Fe-Al.In the present invention
In, the preferred 500-1000r/min of rotating speed of the constant temperature stirring.
In the present invention, in the step (3) the 3rd constant temperature aging preferably 50~90 DEG C of temperature, more preferably 60~80
DEG C, most preferably 65~70 DEG C.In the present invention, time preferably 12~36h of the 3rd constant temperature aging, more preferably 20~30h,
Most preferably 24~26h.
The present invention does not have particular/special requirement to the mode of the separation of solid and liquid, separation of solid and liquid well known to those skilled in the art
Mode, is such as separated by filtration, centrifuges, and the solid-liquid separation method used in the embodiment of the present invention is centrifugation.In this hair
In bright, the rotating speed of the centrifugation is 3000~4000r/min.In the present invention, the time of the centrifugation be 5~
15min。
After separation of solid and liquid, the solid that the present invention preferably obtains centrifugation is soaked in water, and is aided with agitator treating.In the present invention
In, the mass ratio of solid and slurry preferably 1 described in the washing process:50~100, more preferably 1:70~90, it is optimal
Select 1:80.In the present invention, the preferred 500-1000r/min of the rotating speed of the stirring.In the present invention, the time of the stirring is excellent
Select 5~15min.
The present invention does not have particular/special requirement to the mode of the drying, using drying mode well-known to those skilled in the art
, such as forced air drying, vacuum drying use forced air drying in the embodiment of the present invention.In the present invention, the temperature of the drying
It is preferred that 100~115 DEG C, more preferably 105~110 DEG C.In the present invention, the time of the drying preferably 6~8h.It is of the invention preferred
The solid obtained after drying is crushed, 200 mesh sieves is crossed, obtains modified alta-mud.
In order to further illustrate the present invention, the method for preparing modified bentonite provided with reference to embodiment the present invention
It is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) bentonite is purified
The pH value for the sodium hexametaphosphate solution that concentration is 0.2mol/L by the aqueous sodium carbonate for being 4wt.% with concentration
Adjust to 7.0；
The above-mentioned pH value of 200mL is adjusted to 7.0 sodium hexametaphosphate solution and mixed with 50g bentonites, it is permanent at 60 DEG C
Temperature stirring 0.5h, then at a temperature of constant temperature is stirred, mixed liquor constant temperature is stood into 1.5h, solid is deposited on bottom；
Supernatant liquid is taken in drying at 105 DEG C, and the bentonite after drying is crushed, 200 mesh sieves is crossed, is purified
Bentonite；
(2) composite pillared dose of hydroxyl Fe-Al preparation
0.1mol/L sodium hydrate aqueous solution is slowly added dropwise to the aluminium chloride that temperature is 80 DEG C, concentration is 0.1mol/L
In the aqueous solution, then the constant temperature aging 24h at 80 DEG C, obtains hydroxyl-aluminum pillared agent；Mole of the aluminium chloride and sodium hydroxide
Than for 1:2；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 80 DEG C, 0.1mol/L iron chloride is slowly added dropwise to institute
State in hydroxyl-aluminum pillared agent, then 3h is stirred at 80 DEG C of constant temperature, then the constant temperature aging 24h at 80 DEG C, obtain hydroxyl Fe-Al and answer
Close column-supporting agent；The mol ratio of the iron chloride and the aluminium chloride is 0.1:1；
(3) it is modified
Purifying bentonite is mixed with water, the purifying bentonite suspension that concentration is 6g/L is configured to；
The purifying bentonite suspension is heated to after 50 DEG C, constant temperature stirring 0.5h, the step (2) is obtained
Composite pillared dose of hydroxyl Fe-Al is added dropwise in the purifying bentonite suspension, and then constant temperature stirs 3h at 50 DEG C, then 70
Constant temperature aging 36h at DEG C；The summation of metal ion mole in composite pillared dose of the hydroxyl Fe-Al and the purifying swelling
The mass ratio of soil is 1.0mmol:1g；
Feed liquid centrifugation after aging is obtained into solid, by the solid and water using mass ratio as 1:70 ratio is mixed into
Row agitator treating, then in drying 7h at 105 DEG C, dried solid is crushed, and is crossed 200 mesh sieves, is obtained modified alta-mud.
XRD tests are carried out to the modified alta-mud of the gained of embodiment 1, Fig. 1 is as a result seen.
Embodiment 2
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al is prepared according to the method described in step (2) in embodiment 1；
(3) it is modified
Purifying bentonite is mixed with water, the purifying bentonite suspension that concentration is 12g/L is configured to；
The purifying bentonite is heated to after 90 DEG C, constant temperature stirring 0.5h, the hydroxyl Fe- that the step (2) is obtained
Composite pillared dose of Al is added dropwise in the purifying bentonite suspension, and then constant temperature stirs 3h, then the perseverance at 50 DEG C at 90 DEG C
Warm aging 12h；The summation of metal ion mole in composite pillared dose of the hydroxyl Fe-Al and the bentonitic matter of purifying
Amount ratio is 1.0mmol:1g；
Feed liquid centrifugation after aging is obtained into solid, by the solid and water using mass ratio as 1:80 ratio is mixed into
Row agitator treating, then in drying 6h at 105 DEG C, dried solid is crushed, and is crossed 200 mesh sieves, is obtained modified alta-mud.
Embodiment 3
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al is prepared according to the method described in step (2) in embodiment 1；
(3) it is modified
Purifying bentonite is mixed with water, the purifying bentonite suspension that concentration is 3g/L is configured to；
The purifying bentonite suspension is heated to after 50 DEG C, constant temperature stirring 0.5h, the step (2) is obtained
Composite pillared dose of hydroxyl Fe-Al is added dropwise in the purifying bentonite suspension, and then constant temperature stirs 3h at 50 DEG C, then 90
Constant temperature aging 24h at DEG C；The summation of metal ion mole in composite pillared dose of the hydroxyl Fe-Al and the purifying swelling
The mass ratio of soil is 1.0mmol:1g；
Feed liquid centrifugation after aging is obtained into solid, by the solid and water using mass ratio as 1:75 ratio is mixed into
Row agitator treating, then in drying 8h at 105 DEG C, dried solid is crushed, and is crossed 200 mesh sieves, is obtained modified alta-mud.
Embodiment 4
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al is prepared according to the method described in step (2) in embodiment 1；
(3) it is modified
Purifying bentonite is mixed with water, the purifying bentonite suspension that concentration is 6g/L is configured to；
The purifying bentonite suspension is heated to after 70 DEG C, constant temperature stirring 0.5h, the step (2) is obtained
Composite pillared dose of hydroxyl Fe-Al is added dropwise in the purifying bentonite suspension, and then constant temperature stirs 3h at 70 DEG C, then 90
Constant temperature aging 12h at DEG C；The summation of metal ion mole in composite pillared dose of the hydroxyl Fe-Al and the purifying swelling
The mass ratio of soil is 1.0mmol:1g；
Feed liquid centrifugation after aging is obtained into solid, by the solid and water using mass ratio as 1:65 ratio is mixed into
Row agitator treating, then in drying 7h at 105 DEG C, dried solid is crushed, and is crossed 200 mesh sieves, is obtained modified alta-mud.
Embodiment 5
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al is prepared according to the method described in step (2) in embodiment 1；
(3) it is modified
Purifying bentonite is mixed with water, the purifying bentonite suspension that concentration is 12g/L is configured to；
The purifying bentonite suspension is heated to after 70 DEG C, constant temperature stirring 0.5h, the step (2) is obtained
Composite pillared dose of hydroxyl Fe-Al is added dropwise in the purifying bentonite suspension, and then constant temperature stirs 3h at 70 DEG C, then 50
Constant temperature aging 36h at DEG C；The summation of metal ion mole in composite pillared dose of the hydroxyl Fe-Al and the purifying swelling
The mass ratio of soil is 1.0mmol:1g；
Feed liquid centrifugation after aging is obtained into solid, by the solid and water using mass ratio as 1:85 ratio is mixed into
Row agitator treating, in drying 8h at 105 DEG C, dried solid is crushed, and is crossed 200 mesh sieves, is obtained modified alta-mud.
Embodiment 6
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al preparation
It is aluminium chloride that 80 DEG C of concentration is 0.1mol/L that 0.1mol/L sodium hydrate aqueous solution, which is slowly added dropwise to temperature,
In the aqueous solution, then the constant temperature aging 24h at 85 DEG C, obtains hydroxyl-aluminum pillared agent；Mole of the aluminium chloride and sodium hydroxide
Than for 1:2；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 75 DEG C, 0.1mol/L iron chloride is slowly added dropwise to institute
State in hydroxyl-aluminum pillared agent, then 3h is stirred at 75 DEG C of constant temperature, then the constant temperature aging 20h at 75 DEG C, obtain hydroxyl Fe-Al and be combined
Column-supporting agent；The mol ratio of the iron chloride and the aluminium chloride is 0.1:1；
(3) the hydroxyl Fe-Al obtained according to the method described in step (3) in embodiment 1 using the step (2) is answered
Close column-supporting agent and be modified the purifying bentonite that the step (1) is obtained.
Comparative example 1
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1, and by pH value be 7.0 hexa metaphosphoric acid
Sodium water solution replaces with water；
(2) composite pillared dose of hydroxyl Fe-Al is prepared according to the method described in step (2) in embodiment 1；
(3) the hydroxyl Fe-Al obtained according to the method described in step (3) in embodiment 1 using the step (2) is answered
Close column-supporting agent and be modified the purifying bentonite that the step (1) is obtained.
XRD tests are carried out to the modified alta-mud of the gained of comparative example 1, Fig. 1 is as a result seen.
Comparative example 2
(1) according to the Methods For Purification bentonite described in step (1) in embodiment 1；
(2) composite pillared dose of hydroxyl Fe-Al preparation
0.1mol/L sodium hydrate aqueous solution is slowly added dropwise to the aluminium chloride that temperature is 80 DEG C, concentration is 0.1mol/L
In the aqueous solution, then constant temperature aging 24h at room temperature, obtains hydroxyl-aluminum pillared agent；Mole of the aluminium chloride and sodium hydroxide
Than for 1:2；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 80 DEG C, 0.1mol/L iron chloride is slowly added dropwise to institute
State in hydroxyl-aluminum pillared agent, then 3h stirred at 80 DEG C of constant temperature, then naturally cool to room temperature, at room temperature constant temperature aging 24h,
Obtain composite pillared dose of hydroxyl Fe-Al；The mol ratio of the iron chloride and the aluminium chloride is 0.1:1；
(3) the hydroxyl Fe-Al obtained according to the method described in step (3) in embodiment 1 using the step (2) is answered
Close column-supporting agent and be modified the purifying bentonite that the step (1) is obtained.
Testing example 1~6, comparative example 1~2 and bentonite original soil are to Cd as follows2+、Cu2+And Pb2+Suction
Attached performance：
(1) 0.1g bentonites to be measured are weighed to add in 100mL No. 1 centrifuge tube, 30mLCd is added into centrifuge tube2+Concentration
For 50mg/L nitric acid cadmium solution；Weigh 0.1g bentonites to be measured to add in 100mL No. 2 centrifuge tubes, added into centrifuge tube
30mLCu2+Concentration is 50mg/L copper-bath；0.05g bentonites to be measured are weighed to add in 100mL No. 3 centrifuge tubes, to
30mLPb is added in centrifuge tube2+Concentration is 50mg/L lead nitrate solution；
(2) 1~No. 3 centrifuge tube is placed in biological shaking table, temperature be 25.0 ± 1.0 DEG C, rotating speed be 230~240r/
Vibrated under min after 2h, the liquid in centrifuge tube is carried out after centrifugal filtration, inductive coupling plasma emission spectrograph is used
(ICP-OES) the content w of heavy metal element in liquid is determined, the clearance of each heavy metal is calculated by following formula：
Test result is shown in Table 1.
The embodiment 1~6 of table 1, comparative example 1~2 and bentonite original soil are to Cd2+、Cu2+And Pb2+Clearance
| Bentonite to be measured | Cd2+Clearance/% | Cu2+Clearance/% | Pb2+Clearance/% |
| Embodiment 1 | 86.0 | 74.1 | 82.0 |
| Embodiment 2 | 80.8 | 67.0 | 81.2 |
| Embodiment 3 | 83.4 | 70.1 | 79.7 |
| Embodiment 4 | 81.9 | 69.6 | 80.2 |
| Embodiment 5 | 84.2 | 75.3 | 80.9 |
| Embodiment 6 | 85.0 | 71.5 | 81.4 |
| Comparative example 1 | 53.7 | 46.1 | 66.3 |
| Comparative example 2 | 79.5 | 68.7 | 78.9 |
| Bentonite original soil | 62.2 | 63.1 | 78.1 |
As shown in Table 1, the modified alta-mud obtained according to method for preparing modified bentonite provided by the present invention is to Cd2+
Adsorptivity be significantly improved, 0.1g modified alta-muds add 30mLCd2+When concentration is in 50mg/L nitric acid cadmium solution,
Cd2+Clearance be 80.8%~86.0%, than bentonite original soil to Cd2+Clearance improve 18.6%~23.8%；This
Outside, bentonite can also be improved to Cu according to preparation method provided by the present invention2+And Pb2+Adsorptivity, be modified using 0.1g
Bentonite adds 30mLCu2+When concentration is in 50mg/L copper-bath, Cu2+Clearance be 67.0%~75.3%, make
30mLPb is added with 0.05g modified alta-muds2+When concentration is in 50mg/L lead nitrate solution, Pb2+Clearance be 79.7%
~82.0%, than bentonite original soil to Cu2+And Pb2+Clearance increase.
In addition, comparative example 1 uses the pure bentonite of water extraction, the modifying agent then prepared using the method described in embodiment 1 is entered
Row is modified, and gained modified alta-mud is to Cd2+、Cu2+And Pb2+Removal effect it is poorer than embodiment 1~6；Comparative example 2 uses six
The sodium metaphosphate aqueous solution purifies bentonite, and prepares composite pillared dose of hydroxyl Mg-Al using conventional method, then using the post
Support agent is modified to bentonite, and it is to Cd2+、Cu2+And Pb2+Clearance it is also lower than embodiment 1~6.As can be seen here, carry
Pure method and the preparation method of modifying agent have an impact for the absorption property of modified alta-mud, sodium hexametaphosphate solution purification
Bentonite and high temperature ageing prepare modifying agent mutual cooperation, are combined with modification procedure, can effectively improve modified alta-mud pair
In Cd2+Adsorptivity, while to Cu2+And Pb2+Adsorptivity also increase.
Fig. 1 is the XRD of the gained modified alta-mud of embodiment 1, the gained modified alta-mud of comparative example 2 and bentonite original soil,
X-ray diffraction wavelength under the same conditions, it can be seen from bragg's formula, the angle of diffraction is smaller, the crystal layer corresponding to it
Spacing is bigger, and the interlamellar spacing of embodiment 1 has increased than comparative example 2 and original soil as shown in Figure 1, illustrates provided by the present invention
Method can increase bentonite bed spacing, and then improve bentonite to Cd2+Adsorptivity.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method for preparing modified bentonite, comprises the following steps：
(1) bentonite is purified with sodium hexametaphosphate solution, obtains purifying bentonite；
(2) sodium hydrate aqueous solution is added dropwise in 70~90 DEG C of aluminum saline solution, then remains temperature-resistant and carry out first
Constant temperature aging, obtains hydroxyl-aluminum pillared agent；
Under conditions of the temperature of the hydroxyl-aluminum pillared agent is 70~90 DEG C, molysite aqueous solution is added dropwise to the hydroxy Al post
Support in agent, then maintain the second constant temperature aging of temperature-resistant progress, obtain composite pillared dose of hydroxyl Fe-Al；
(3) the 3rd constant temperature aging is carried out after the purifying bentonite is mixed with composite pillared dose of the hydroxyl Fe-Al, is obtained
Modified alta-mud；
There is no the restriction of time sequencing between the step (1) and step (2).
2. preparation method as claimed in claim 1, it is characterised in that the purification in the step (1) comprises the following steps：
The bentonite is mixed with the sodium hexametaphosphate solution, constant temperature stirs 0.5~1.5h at 50~70 DEG C, obtains
Mixed liquor；
At a temperature of the constant temperature is stirred, the mixed liquor is subjected to stratification, obtained supernatant liquid is dried
To purifying bentonite.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the concentration of the sodium hexametaphosphate solution is
0.15~0.35mol/L, pH value is 6.5~7.5.
4. preparation method as claimed in claim 1 or 2, it is characterised in that the bentonitic quality and the hexa metaphosphoric acid
The volume ratio of sodium water solution is 1g:3~4mL.
5. preparation method as claimed in claim 1, it is characterised in that the Al in the aluminum saline solution3+, the sodium hydroxide
With the Fe in the molysite aqueous solution3+Mol ratio be 1:1.7~2.2:0.05~0.15.
6. preparation method as claimed in claim 1, it is characterised in that in the step (2), molysite aqueous solution is added dropwise to
In the hydroxyl-aluminum pillared agent, the temperature of the hydroxyl-aluminum pillared agent is maintained, constant temperature stirs 2.5~4h, then carries out the second constant temperature
Aging.
7. the preparation method as described in claim 1 or 6, it is characterised in that the first constant temperature aging and in the step (2)
The time of two constant temperature agings independently is 20~30h.
8. preparation method as claimed in claim 1, it is characterised in that in the step (3), composite pillared dose of hydroxyl Fe-Al
The amount of the total material of middle metal ion is 1.0~1.5mmol with the bentonitic mass ratio of purifying:1g.
9. preparation method as claimed in claim 1, it is characterised in that the step (3) specifically includes following steps：
The purifying bentonite is mixed with water, obtains purifying bentonite suspension；
Under conditions of the temperature of the purifying bentonite suspension is 50~90 DEG C, the hydroxyl that the step (2) is obtained
Composite pillared dose of Fe-Al is added dropwise in the purifying bentonite suspension, then maintains the temperature of the purifying bentonite suspension
Degree, constant temperature stirs 2.5~4.0h, then carries out the 3rd constant temperature aging；
The feed liquid that the 3rd constant temperature aging is obtained obtains modified alta-mud through separation of solid and liquid, washing, drying.
10. the preparation method as described in claim 1 or 9, it is characterised in that the temperature of the 3rd constant temperature aging in the step (3)
Spend for 50~90 DEG C, the time of the 3rd constant temperature aging is 12~36h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001377A (en) * | 2019-12-04 | 2020-04-14 | 青岛科技大学 | Iron-zirconium-aluminum combined column-supported bentonite composite material and preparation method thereof |
| KR20220146871A (en) * | 2021-04-26 | 2022-11-02 | 한국전력공사 | Composition for carbon dioxide sorbent, manufacturing method for carbon dioxide sorbent using the same, and carbon dioxide sorbent manufactured using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239307A (en) * | 2008-03-17 | 2008-08-13 | 昆明理工大学 | Method for preparing carbon monoxide translating catalyst |
| CN101306863A (en) * | 2008-07-04 | 2008-11-19 | 绍兴文理学院 | Finishing agent for modified bentonite and zero-valent molten iron |
| US20100108616A1 (en) * | 2007-01-25 | 2010-05-06 | Geo Grounding Engineering Operations | Chemical composition and process for treating geotechnical slurries |
| CN101708557A (en) * | 2009-11-24 | 2010-05-19 | 江苏工业学院 | Method for preparing magnetic nanometer metal particle for degrading organic pollutant in waste water |
| CN106179193A (en) * | 2016-08-30 | 2016-12-07 | 内蒙古师范大学 | A kind of polymerization iron carbonyl modified kaolin composite and its preparation method and application |
-
2017
- 2017-04-18 CN CN201710254734.6A patent/CN107159098A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100108616A1 (en) * | 2007-01-25 | 2010-05-06 | Geo Grounding Engineering Operations | Chemical composition and process for treating geotechnical slurries |
| CN101239307A (en) * | 2008-03-17 | 2008-08-13 | 昆明理工大学 | Method for preparing carbon monoxide translating catalyst |
| CN101306863A (en) * | 2008-07-04 | 2008-11-19 | 绍兴文理学院 | Finishing agent for modified bentonite and zero-valent molten iron |
| CN101708557A (en) * | 2009-11-24 | 2010-05-19 | 江苏工业学院 | Method for preparing magnetic nanometer metal particle for degrading organic pollutant in waste water |
| CN106179193A (en) * | 2016-08-30 | 2016-12-07 | 内蒙古师范大学 | A kind of polymerization iron carbonyl modified kaolin composite and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 刘新宇，: ""羟基铁及羟基铁铝柱撑膨润土在废水处理中的应用研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 许小龙，: ""膨润土钠化改性和无机柱撑的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001377A (en) * | 2019-12-04 | 2020-04-14 | 青岛科技大学 | Iron-zirconium-aluminum combined column-supported bentonite composite material and preparation method thereof |
| CN111001377B (en) * | 2019-12-04 | 2022-11-01 | 青岛科技大学 | Iron-zirconium-aluminum combined column-supported bentonite composite material and preparation method thereof |
| KR20220146871A (en) * | 2021-04-26 | 2022-11-02 | 한국전력공사 | Composition for carbon dioxide sorbent, manufacturing method for carbon dioxide sorbent using the same, and carbon dioxide sorbent manufactured using the same |
| KR102562021B1 (en) | 2021-04-26 | 2023-08-01 | 한국전력공사 | Composition for carbon dioxide sorbent, manufacturing method for carbon dioxide sorbent using the same, and carbon dioxide sorbent manufactured using the same |
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