CN110054194A - A kind of inorganic gel materials and preparation method thereof - Google Patents
A kind of inorganic gel materials and preparation method thereof Download PDFInfo
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- CN110054194A CN110054194A CN201811155056.9A CN201811155056A CN110054194A CN 110054194 A CN110054194 A CN 110054194A CN 201811155056 A CN201811155056 A CN 201811155056A CN 110054194 A CN110054194 A CN 110054194A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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Abstract
The invention discloses a kind of inorganic gel materials and preparation method thereof, which includes montmorillonite and palygorskite, it is preferable that further includes acids electrolyte, the preparation method of the inorganic gel materials includes the following steps: (1) to prepare montmorillonite and palygorskite；Step 2 mixes montmorillonite and palygorskite with water, obtains suspension；Step 1 gained suspension is carried out aging process by step 3, it is preferable that further include: acids electrolyte is added in step 4.Montmorillonite and palygorskite form piece-stick overlapping overlapped structure in inorganic gel materials of the invention, and under the electrolytelike regulation of acid, excellent gelling performance is obtained, and the preparation method simple process of the inorganic material, raw material are easy to get, is suitable for large-scale industrialization promotion.
Description
Technical field
The present invention relates to a kind of gel rubber materials and preparation method thereof, and in particular to a kind of inorganic gel materials and its preparation side
Method.
Background technique
Inorganic gel materials are the slurries formed after it is mixed and stirred with water or aqueous solution using inorganic mineral as main component,
By a series of physical chemical change, and other materials is cemented to the entirety with intensity.
Montmorillonite gelling is a kind of product obtained by bentonite raw ore deep processing, can be used as thickener, suspending agent and steady
Agent is determined, in household chemicals industry (toothpaste and cosmetics carrier), fine chemistry industry (catalyst carrier), pharmaceuticals industry (in drug
Mesosome) etc. extensive applications.
Montmorillonite is a kind of layer silicate mineral, and crystal structure is by pressing from both sides one layer of alumina among two layers of oxygen-octahedron
It is octahedra.Since each interionic of montmorillonite intracell has the phenomenon that class matter is with mutually replacing, when Al3+ replaces Si4+, chip
Surface has permanent negative electrical charge, therefore the cations such as K+, Na+, Ca+, Mg+, H+ in adsorbable environment.In interlamination region,
Since cationic ambient absorption has hydrone and the hydration of its own, expand chip on c-axis lamella point
It opens and destroys montmorillonite lattice structure, after sodium, the interlayer charge of montmorillonite changes, and lamella is uniformly dispersed in water, piece
Layer surface is negatively charged, and end face is positively charged, and under electrostatic interaction, lamella mutually overlaps in water, and being formed, there is end-face to connect
Card room formula structure montmorillonite inorganic gel.However, the gelling performance of montmorillonite gelling needs to be further increased.
Palygorskite (also known as attapulgite) is a kind of aqueous rich magnesium aluminosilicate clays mineral for having chain layer structure, knot
There are crystal lattice in structure, variable amount of Na is contained in crystal+、Ca+、Fe3+、Al3+, crystal is at needle-shaped, fibrous or fiber collection
Close shape.There is salt resistance, high temperature resistant property and higher viscosity after palygorskite clay aquation, be widely used in inland both at home and abroad containing saline land
Layer drilling well, marine drilling, ultra-deep well drilling, geothermal drilling and molecular sieve molded binder, the suspension stabilizer of coatings industry.
In addition to this, palygorskite it is more be applied to fire proofing, light industry (papermaking), textile industry (dye suspension agent), (washing helps daily use chemicals
Agent and cosmetics carrier) and fire proofing etc..
Due to montmorillonite and palygorskite it is special crystal structure and the two be similar physical and chemical and processing performance, by montmorillonite
It can superior inorganic gel materials with the compound available of palygorskite.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, and montmorillonite and palygorskite are mixed and led to water
Peracid electrolyte adjustment and control system pH value, obtains inorganic gel materials, montmorillonite and palygorskite are formed in the inorganic gel materials
The mutual support structure that piece-stick combines assigns inorganic gel materials excellent gelling performance, and gelling performance is with system pH
It reduces and enhances, thereby completing the present invention.
One aspect of the present invention is to provide a kind of inorganic gel materials, which includes montmorillonite and slope thread
Stone.
Wherein, in inorganic gel materials the mass ratio of montmorillonite and palygorskite be 1:9~9:1, preferably 6:4~9:1,
More preferably 7:3~9:1.
Wherein, the partial size of the montmorillonite is more than 200 mesh, and the partial size of the palygorskite is more than 200 mesh.
Wherein, which further includes acids electrolyte,
Preferably, acids electrolyte is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid.
Another aspect of the present invention provides a kind of preparation method of inorganic gel materials, wherein method includes the following steps:
Step 1 prepares montmorillonite and palygorskite；
Step 2 mixes montmorillonite and palygorskite with water, obtains suspension；
Step 1 gained suspension is carried out aging process by step 3.
Wherein, in step 2, the solid content of the suspension is 2%~10%, preferably 4%~8%, more preferably 4%
~6%,
The mixed mode is stirring, and the speed of stirring is 10000~15000r/min, preferably 10000~
13000r/min, more preferably 11000r/min, and
The time of stirring be 10~40min, preferably 15~30min, more preferably 18~25min,
In step 3, the temperature of the aging process is 15~35 DEG C, preferably 20~30 DEG C, such as 25 DEG C of room temperature,
The time of the aging process is 10~30h, preferably 12~20h, more preferably 16h.
The preparation method further include: acids electrolyte is added in step 4,
Wherein, acids electrolyte is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid.
In step 4, after acids electrolyte is added, the Zeta potential of system is 10~25mV, preferably 17~21mV, more excellent
It is selected as 20~21mV.
Provided inorganic gel materials according to a first aspect of the present invention are preferably made as provided by second aspect of the present invention
Preparation Method is made.
The invention has the benefit that
(1) inorganic gel materials provided by the invention have excellent gelling performance, and its gelling performance can be by adding
Enter acids electrolyte to be regulated and controled, such as after being regulated and controled with dilute sulfuric acid, compared with montmorillonite inorganic gel materials, montmorillonite-slope
The apparent viscosity and surface Zeta potential of thread stone composite inorganic gel rubber material have been respectively increased 7.3% and 10.3% or more；
(2) lamellar structure of montmorillonite and the club shaped structure of palygorskite are mutually tied in inorganic gel materials provided by the invention
It closes, forms piece-stick overlapping overlapped the structure mutually supported, improve the gelling performance of inorganic gel materials, and with system
The reduction of PH, combination degree enhancing, gelling performance further increase.
(3) inorganic gel materials provided by the invention are made by montmorillonite and palygorskite, and the preparation method is simple, raw material is easy
It obtains, is low in cost, being conducive to large-scale industrialization promotion；
(4) preparation method simple process, the energy conservation and environmental protection of inorganic gel materials provided by the present invention.
Detailed description of the invention
Fig. 1 shows the XRD spectra of 1 gained sample 1-1 of embodiment；
Fig. 2 shows the TEM of 1 gained sample 1-1 of embodiment figures；
Fig. 3 shows the XRD spectra of 2 gained sample 2-1 of embodiment；
Fig. 4 shows the TEM figure of 2 gained sample 2-1 of embodiment；
Fig. 5 shows the XRD spectra of 3 gained sample 3-1 of embodiment；
Fig. 6 shows the TEM figure of 3 gained sample 3-1 of embodiment；
Fig. 7 shows the XRD spectra of 3 gained sample 3-2 of embodiment；
Fig. 8 shows the TEM figure of 3 gained sample 3-2 of embodiment；
Fig. 9 shows the XRD spectra of 3 gained sample 3-3 of embodiment；
Figure 10 shows the TEM figure of 3 gained sample 3-3 of embodiment；
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
An aspect of of the present present invention provides a kind of inorganic gel materials, which includes montmorillonite and slope thread
Stone.
In the present invention, inorganic gel materials can be made by the inorganic gel materials.
According to the present invention, in inorganic gel materials the mass ratio of montmorillonite and palygorskite be 1:9~9:1, preferably 6:4~
9:1, more preferably 7:3~9:1.
Montmorillonite is bentonitic main component, and montmorillonite gelling is the product obtained by bentonite raw ore deep processing.
According to the present invention, montmorillonite is made by raw ore of calcium base bentonite.
According to the present invention, montmorillonite is obtained by calcium-base bentonite through roughing, aquation, screening, sodium, drying, crushing.
According to the present invention, raw ore of calcium base bentonite is subjected to roughing and obtains calcium-base bentonite concentrate, that is, calcium base essence soil.
In the present invention, the raw ore of calcium base bentonite for being smectite content 30%~80% is used, raw ore is carried out thick
Choosing processing, removes the impurity in raw ore.
According to the present invention, hydration process is carried out to calcium base essence soil, obtains the native suspension of calcium base essence.
In the present invention, carrying out hydration process to calcium base essence soil may make that montmorillonite chip occurs on C axis in calcium base essence soil
Expansion separates lamella, expands montmorillonite, destroys the lattice structure of montmorillonite, does standard for subsequent progress ion exchange
It is standby.
According to the present invention, it is sieved after native aquation smart to calcium base.
According to the present invention, the native suspension of calcium base essence after screening is subjected to sodium modification, sodium modification is by calcium base swelling
Soil is modified as sodium bentonite.
Due to high-valence cationic (Ca2+, Mg2+Deng) hydration shell is thin, expansion multiple is low, and cation exchange capacity (CEC) is small,
Cation (Na at a low price+, K+) aquation film thickness, expansion multiple is high, and CEC is big.Sodium bentonite has higher compared with calcium-base bentonite simultaneously
Water absorption rate and thermal stability, stronger plasticity and caking property and superior suspension thixotropy, therefore it is solidifying in preparation
When glue, need calcium-base bentonite being modified as sodium bentonite.
According to the present invention, sodium reagent used in sodium modification is sodium salt, is selected from sodium carbonate, sodium chloride, sodium phosphate, hydrogen-oxygen
Change one or more of sodium, sodium fluoride, preferably one or more of sodium carbonate, sodium chloride, sodium hydroxide, more preferably
Sodium carbonate or sodium chloride, such as sodium chloride.
According to the present invention, sodium salt is added in the native suspension of calcium base essence and be stirred continuously, make that montmorillonite is fully dispersed, expansion
And realize sodium.
In the present invention, after calcium-base bentonite carries out sodium modification, the adsorbed Ca of interlayer2+, Mg2+Deng by Na+It is replaced, i.e.,
Cation exchange reaction occurs, causes the interlayer charge of montmorillonite to change, lamella is uniformly dispersed in water, sheet surfaces band
Negative electrical charge, end face is positively charged, and under electrostatic interaction, lamella mutually overlaps in water, forms " card room formula " knot that end-face connects
Structure.
In the present invention, it dry, pulverize after sodium processing, be sieved to obtain montmorillonite.
Palygorskite is also known as attapulgite, Palygorskite, is a kind of aqueous rich magnesium manosil AS with fibrous strands layer structure
Salt clay mineral contains variable amount of Na+, Ca+, Fe3+, Al3+, crystal knot in crystal there are crystal lattice in structure
Structure is in needle-shaped, fibrous or fiber set shape.
In the present invention, the length of palygorskite is 0.1~5 μm, preferably 0.5~3 μm, such as the short crystalline substance that length is 1~2 μm
Beam palygorskite.
According to the present invention, palygorskite is made by palygorskite raw ore.
One kind being preferably carried out mode, and palygorskite is obtained by the roughing of palygorskite raw ore, purification, drying, crushing, sieving.
In the present invention, inorganic gel materials are the composite suspension liquid for including montmorillonite and palygorskite, the stability of suspension
By the surface Zeta potential of montmorillonite and palygorskite particle come standard, the absolute value of surface Zeta potential is higher, suspension it is steady
It is qualitative better.
According to the present invention, montmorillonite partial size is 200 mesh or more, more than preferably 300 mesh.
According to the present invention, palygorskite partial size is 200 mesh or more, more than preferably 300 mesh.
It according to the present invention, is at 6.49 °, 19.8 ° and 61.8 ° there are crystallographic plane diffraction peak in 2 θ in the XRD spectrum of montmorillonite,
There are crystallographic plane diffraction peaks at 2 θ is 8.50 °, 19.8 ° and 61.8 ° in the XRD spectrum of palygorskite.
It according to the present invention, further include acids electrolyte in the inorganic gel materials.
According to invention, acids electrolyte be preferably selected from one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid or
It is several, it is more preferably selected from one or more of hydrochloric acid, sulfuric acid and phosphoric acid, most preferably sulfuric acid, such as dilute sulfuric acid.
According to the present invention, which is prepared by montmorillonite and palygorskite, can be denoted as montmorillonite-palygorskite
Composite inorganic gel rubber material.
According to the present invention, compared with the XRD spectrum of individual montmorillonite and palygorskite, the compound nothing of montmorillonite-palygorskite
The characteristic peak of montmorillonite and palygorskite in the XRD spectrum of machine gel rubber material disappears, and the apparent viscosity of the inorganic gel materials is
1150mPa/s or more, preferably 1200mPa/s or more, most preferably 1250mPa/s；The surface Zeta of the inorganic gel materials
The absolute value of current potential is in 15mV or more, more preferably in 18mV or more, most preferably in 20mV or more.
Another aspect of the present invention provides a kind of preparation method of inorganic gel materials, preferably prepares first party of the present invention
The method of inorganic gel materials described in face more preferably prepares montmorillonite-palygorskite inorganic gel materials method, this method
The following steps are included:
Step 1 prepares montmorillonite and palygorskite；
According to the present invention, in step 1, montmorillonite and palygorskite are preferably montmorillonite described in first aspect present invention and slope
Thread stone.
According to the present invention, in step 1, montmorillonite is by calcium-base bentonite through roughing, aquation, screening, sodium, drying, crushing
It obtains.
According to the present invention, in step 1, palygorskite is obtained by the roughing of palygorskite raw ore, purification, drying, crushing, sieving.
According to the present invention, in step 1, the partial size of montmorillonite and palygorskite is 200 mesh or more, more than preferably 300 mesh.
Step 2 mixes montmorillonite and palygorskite with water, obtains suspension；
According to the present invention, in step 2, the mass ratio of montmorillonite and palygorskite is 1:9~9:1, preferably 6:4~9:1, more
Preferably 7:3~9:1.
According to the present invention, in step 2, the solid content of suspension is 2%~10%, preferably 4%~8%, more preferably
4%~6%.
According to the present invention, in step 2, hybrid mode is preferably high-speed stirred, and mixing speed is 10000~15000r/
Min, preferably 10000~13000r/min, more preferably 11000r/min and mixing time be 10~40min, preferably 15
~30min, more preferably 18~25min.
According to the present invention, in step 2, wet concentration is from one of deionized water or distilled water.
According to the present invention, in step 2, distilled water is added into reactor (such as agitator), weighs illiteracy in mass ratio
Montmorillonite and palygorskite, are preferably uniformly mixed, under conditions of high-speed stirred, by montmorillonite and palygorskite by de- stone and palygorskite
Mixture be added in distilled water, stirring dispersed, obtain montmorillonite-palygorskite suspension.
In the present invention, montmorillonite is added to the water, montmorillonite lamella is uniformly dispersed in water, and sheet surfaces are negatively charged
Lotus, end face is positively charged, and under electrostatic interaction, lamella mutually overlaps in water, forms the card room formula structure that end-face connects, and
The crystal of palygorskite is added to the water in rodlike, needle-shaped, fibrous or fiber set shape, palygorskite, forms connected head-to-tail heap
Build structure, viscosity with higher and salt resistance, high temperature resistant property.
The inventors discovered that since montmorillonite and palygorskite have a similar physicochemical property, such as cationic interchangeability,
Montmorillonite and palygorskite are dispersed in water by water imbibition, adsorption bleaching, big specific surface area and colloid index and expansion capacity simultaneously
In, " the card room formula " structure of montmorillonite and the connected head-to-tail packing structure of palygorskite change, and are bound to each other to form and mutually mix
The network structure intersect, mutually supported, can be obtained the good montmorillonite of network structure strength and stability-palygorskite suspension, into
And obtain the excellent montmorillonite of gelling performance-palygorskite inorganic gel materials.
According to the present invention, more uniform to disperse montmorillonite and palygorskite in water, montmorillonite and palygorskite it is mixed
Closing object can be added to the water in batches, such as divide three to five additions, but need to all be added in 1min.Due in high-speed stirred
In the process, montmorillonite and palygorskite are easily adhered on the reactor wall, such as the montmorillonite not in time by attachment on the reactor wall
It is removed with palygorskite, then will affect the solid content of suspension and the stability of suspension etc., and then influence final gel rubber material
Performance.
Therefore, according to the present invention, in high-speed agitating process, every 5~10min, stop stirring, reactor will be adhered to
Montmorillonite and palygorskite on wall are scraped in suspension with scraper, are further continued for stirring.
Step 2 gained suspension is carried out aging process by step 3.
According to the present invention, in step 3, aging process is carried out to step 2 gained suspension, obtains the suspension of aging,
In, the temperature of aging process is 15~35 DEG C, preferably 20~30 DEG C, such as 25 DEG C of room temperature,
According to the present invention, the time of aging process is 10~30h, preferably 12~20h, more preferably 16h.
In the present invention, montmorillonite-palygorskite composite suspension liquid passes through aging process, montmorillonite can be made to occur in water molten
Swollen, i.e. hydration swelling keeps montmorillonite lamella well separated, destroys the lattice structure of montmorillonite, so as to form phase with palygorskite
The piece mutually supported-stick network structure.Aging process needs the regular hour, and aging treatment time is short, and montmorillonite lamella is not abundant
It separates, so that network structure can not be formed with palygorskite.
According to the present invention, in step 3, must be interfered to exclude various extraneous factors, aging process in sealed environment into
Row.
According to the present invention, preparation method further include: acids electrolyte is added in step 4.
Zeta potential is the important indicator for characterizing stability of suspension, and the Zeta potential absolute value of suspension surface is particle
Between mutually exclusive or attraction intensity measurement, the absolute value of the Zeta potential of suspension surface is higher, suspension it is steady
It is qualitative better.
The inventors discovered that in montmorillonite-palygorskite suspension by aging process, montmorillonite and palygorskite particle table
There are negative electrical charges in face cannot reach good gelling performance since the two surface potential cannot be well matched with, so needing to adjust
The montmorillonite and palygorskite particle surface Zeta potential in suspension are controlled, to improve the stability of suspension, obtains montmorillonite-
Palygorskite inorganic gel materials.
The inventors discovered that the Zeta potential absolute value on montmorillonite-palygorskite composite suspension liquid sample surface is with body
It is that pH value reduces and increases, and the absolute value of its gelling performance and surface Zeta potential is positively correlated.For example, being in solid content
Be added the sulfuric acid of the 0.1mol/L of 9ml in montmorillonite-palygorskite suspension, the absolute value of the surface Zeta potential of suspension compared with
The suspension that sulfuric acid is not added improves 13% or more, and the suspension of sulfuric acid is not added and improves for the apparent viscosity of suspension
3.9 times or more.
According to the present invention, in step 4, acids electrolyte, stirring is added in the suspension after resulting aging in step 2
Uniformly, montmorillonite-palygorskite inorganic gel materials are obtained.
According to the present invention, inorganic gel materials described in first aspect present invention and according to nothing obtained by second aspect of the present invention
Machine gel rubber material, as montmorillonite-palygorskite composite inorganic gel rubber material, the composite inorganic gel rubber material preferably include to cover de-
Stone, palygorskite, water and acids electrolyte, the state of the inorganic gel materials is gel state, also referred to as inorganic gel body at room temperature
System.
According to the present invention, in step 4, acids electrolyte is in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid
One or more are preferably selected from one or more of hydrochloric acid, sulfuric acid and phosphoric acid, more preferably sulfuric acid, such as dilute sulfuric acid.
According to the present invention, in step 4, after acids electrolyte is added, the pH of system is less than 3.Such as when addition 3ml's
After the sulfuric acid of 0.1mol/L, the pH of system is 2.7, and after the sulfuric acid of 0.1mol/L of 9ml is added, the pH of system is 2.22.
According to the present invention, in step 4, after addition acids electrolyte in obtained montmorillonite-palygorskite composite suspension liquid
The absolute value of the surface Zeta potential of montmorillonite and palygorskite be 10~25mV, preferably 17~21mV, more preferably 20~
21mV。
Inorganic gel materials, i.e. montmorillonite-palygorskite of first aspect present invention offer are obtained according to method made above
Composite inorganic gel rubber material is at 6.49 °, 19.8 ° and 61.8 ° in 2 θ in the XRD spectrum of the composite inorganic gel rubber material
The diffraction maximum of montmorillonite and the diffraction maximum of the palygorskite at 8.50 °, 19.8 ° and 61.8 disappear, and illustrate in montmorillonite-slope thread
In stone composite inorganic gel rubber material, respectively crystallization degree is deteriorated for montmorillonite and palygorskite, forms the piece-stick overlapping mutually supported
Bridging arrangement causes the lattice structure of composite inorganic gel rubber material to change, no characteristic diffraction peak.
The apparent viscosity of the inorganic gel materials be 1150mPa/s or more, preferably 1200mPa/s or more, most preferably
1250mPa/s or more；The surface Zeta potential of the inorganic gel materials is 20mV or more.
Tem analysis is carried out to the samples of inorganic gel materials, finds in the inorganic gel materials sheet montmorillonite and rodlike
The overlapped overlap joint of palygorskite, also, when regulating and controlling to system pH, with the reduction of system pH, montmorillonite and slope thread
Piece-stick overlapping overlap joint degree enhancing of stone, shows excellent gelling performance.For example, in montmorillonite-palygorskite suspension
The dilute sulfuric acid of 9ml 0.1mol/L is added, stirs evenly, the gelling performance of inorganic gel materials is tested, it is inorganic to measure this
The apparent viscosity of gel rubber material can reach 1283.2mPa/s, and the absolute value of surface Zeta potential reaches 20.6mV, thus illustrates,
Montmorillonite and palygorskite form the network structure mutually supported in the inorganic gel materials, so that inorganic gel materials are with excellent
Different gelling performance.
Another aspect of the invention provides a kind of purposes of inorganic gel materials, is used to prepare inorganic gel, main to apply
In fields such as water paint, dry powder and mortar, aqueous agricultural-chemical, oilfield additive, animal feed, medicine, cosmetics.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection scope of invention constitutes any restrictions.
The test method that the embodiment of the present application uses is as follows:
XRD test:
The preparation of sample: being dripped to a small amount of suspension or gel sample on XRD sample stage with dropper, flattened with sheet glass,
It is tested.
Test equipment: Bruker Scientific Instruments Hong Kong CO., Limited production
D8Advance X-ray diffractometer (Cu target K alpha ray), in λ=0.15418nm, step width=0.02, operating voltage 40kV, work
Sample is analyzed under the conditions of electric current 40mA.
And it is compared with standard card, wherein Montmorillonite, PDF#13-0135 are na-montmorillonite standard
PDF card, palygorskite, PDF#31-0876 are palygorskite standard PDF card.
TEM test
The preparation of sample: minute quantity gel sample is distributed in deionized water (mass fraction about a ten thousandth), sufficiently
After concussion, then ultrasonic disperse 15min drips to carbon nanometer net surface, makes moisture natural evaporation that sample be made in culture dish.
Test equipment: the 2 type transmission electron microscope of H-8100 of Hitachi, Japan production, acceleration voltage: 200kV
Apparent viscosity test:
The preparation of sample: gel sample being poured into the specimen cup of viscosimeter outfit, directly progress test reading.
Test equipment: the NDJ-8S rotational viscometer of the upper sub- instrument company of Nereid's atmospheric electricity
Test condition: rotary viscosity metering rotating speed 60r/min, 25 ± 1 DEG C of environment temperature.
The test of surface Zeta potential:
The preparation of sample: being distributed in water (mass fraction is about one thousandth) for gel sample, after fulling shake, ultrasound
Disperse 15min and sample is made, is then added in Zeta potential Special sample pond and is tested with disposable dropper.
Test equipment: the Zetasizer Nano ZS90 of Malvern Instr Ltd., Britain
Test condition: 25 DEG C of temperature, decentralized medium is water, sample cell model 1070.
Embodiment 1
To raw ore of calcium base bentonite roughing, aquation, screening, sodium, drying, crushing and 200 meshes are crossed, obtain montmorillonite；
It measures distilled water 300ml to be fitted into agitator, under 11000r/min stirring, while be slowly added into agitator
15 grams of montmorillonites, continue to stir, remove agitator every 5~10min halfway, are scraped the montmorillonite being sticked on barrel wall with scraper
In agitator, mixing time 20min obtains montmorillonite suspension；
At 25 DEG C of room temperature, above-mentioned montmorillonite suspension is put into aging process 16h in container, the montmorillonite after obtaining aging
Suspension.It is stirred into 3min at 1000r/min, is denoted as sample 1-1, tests its surface viscosity and surface Zeta potential, and
XRD and TEM test is carried out to it；
Into the montmorillonite suspension after aging be added 9ml 0.1mol/L dilute sulfuric acid, stir evenly, obtain montmorillonite without
Machine gel rubber material is denoted as sample 1-2, tests its apparent viscosity and surface Zeta potential.
It will be seen from figure 1 that in montmorillonite suspension in the XRD spectrum of montmorillonite 2 θ be 6.49 °, 19.8 ° and 61.8 °
There are crystallographic plane diffraction peaks at place.And diffraction maximum is in widthization trend.
Figure it is seen that montmorillonite is the laminated structure of expansion in montmorillonite suspension, illustrate that hydration makes to cover
De- flag is lifted off of, and is in single sheet, piece diameter is having a size of 0.2~1 μm.
Embodiment 2
To the roughing of palygorskite raw ore, purification, drying, crushing and 200 meshes are crossed, obtain short brilliant beam palygorskite；
It measures distilled water 300ml to be fitted into agitator, under 11000r/min stirring, while be slowly added into agitator
15 grams of palygorskites, continue to stir, remove agitator every 5~10min halfway, are scraped the palygorskite being sticked on barrel wall with scraper
In agitator, mixing time 20min obtains palygorskite suspension；
At 25 DEG C of room temperature, above-mentioned palygorskite suspension is put into aging process 16h in container, the palygorskite after obtaining aging
Suspension.It is stirred into 3min at 1000r/min, is denoted as sample 2-1, tests its surface viscosity and surface Zeta potential, is surveyed
Test result is as shown in table 1, and XRD test and TEM test are carried out to it, and test result difference is as depicted in figs. 1 and 2；
9ml 0.1mol/L dilute sulfuric acid is added into the palygorskite suspension after aging, stirs evenly, is denoted as sample 2-2,
It tests its apparent viscosity and surface Zeta potential, test result is as shown in table 1.
From figure 3, it can be seen that in palygorskite suspension in the XRD spectrum of palygorskite 2 θ be 8.50 ° and 19.8 ° with
There are crystallographic plane diffraction peaks at 61.8 °.And diffraction maximum is in widthization trend.
From fig. 4, it can be seen that palygorskite is in rodlike or fibrous structure, due to hydration, palygorskite crystalline substance beam is dissociated
At monocrystalline beam, length is 1~2 μm, stick diameter about 10nm.
Embodiment 3
To raw ore of calcium base bentonite roughing, aquation, screening, sodium, drying, crushing and 200 meshes are crossed, obtain montmorillonite；
To the roughing of palygorskite raw ore, purification, drying, crushing and 200 meshes are crossed, obtain short brilliant beam palygorskite；
It measures distilled water 300ml to be fitted into agitator, under 11000r/min stirring, while be slowly added into agitator
The mixture (wherein, the mass ratio of montmorillonite and palygorskite is 9:1) of 15 grams of montmorillonites and palygorskite, continues to stir, halfway often
Agitator is removed every 5~10min, is scraped the montmorillonite being sticked on barrel wall or palygorskite in agitator with scraper, mixing time
For 20min, montmorillonite-palygorskite suspension is obtained；
At 25 DEG C of room temperature, above-mentioned montmorillonite-palygorskite suspension is put into aging process 16h in container, after aging
Montmorillonite-palygorskite suspension stirs 3min at 1000r/min, is denoted as sample 3-1, tests its surface viscosity and surface Zeta
Current potential, the results are shown in Table 1, and XRD and TEM test is carried out to it, and test result difference is as shown in Figure 5 and Figure 6；
3ml 0.1mol/L dilute sulfuric acid is added into the montmorillonite after aging-palygorskite suspension, stirs evenly, is denoted as sample
Product 3-2 tests its apparent viscosity and surface Zeta potential, and test result is as shown in table 1, and XRD and TEM test is carried out to it,
Test result difference is as shown in Figure 7 and Figure 8；
6ml 0.1mol/L dilute sulfuric acid is continuously added into sample 3-2, is stirred evenly, and it is inorganic to obtain montmorillonite-palygorskite
Gel rubber material is denoted as sample 3-3, tests its apparent viscosity and surface Zeta potential, and test result is as shown in table 1, to sample 3-3
XRD and TEM test is carried out, test result difference is as shown in Figure 9 and Figure 10.
Table 1
| Sample | Apparent viscosity (mPa/s) | Surface Zeta potential (mV) |
| 1-1 | 284.7 | -18.667 |
| 1-2 | 1195.0 | -19.533 |
| 2-1 | 350.2 | -12.033 |
| 2-2 | 309.3 | -11.433 |
| 3-1 | 261.1 | -18.200 |
| 3-2 | 519.6 | -16.967 |
| 3-3 | 1283.2 | -20.600 |
From table 1 it follows that seeing on the whole, the apparent viscosity and surface Zeta potential of suspension or inorganic gel materials
The variation tendency that absolute value is substantially positively correlated, not plus when dilute sulfuric acid, montmorillonite-palygorskite suspension apparent viscosity and surface
Zeta potential absolute value is below montmorillonite suspension.
When the dilute sulfuric acid of 3ml 0.1mol/L is added in the montmorillonite to after aging-palygorskite suspension, gained 3-2 sample
The apparent viscosity of product improves nearly 1 times compared with sample 3-1；After 9ml 0.1mol/L dilute sulfuric acid is added into suspension, obtain
To inorganic gel materials, gained montmorillonite-palygorskite inorganic gel materials (sample 3-3) apparent viscosity mentioning than sample 3-1
3.9 times or more high, gained montmorillonite-palygorskite inorganic gel materials apparent viscosity and surface Zeta potential absolute value are obvious
Higher than single montmorillonite inorganic gel materials.
Illustrate after dilute sulfuric acid is added in montmorillonite-palygorskite suspension, montmorillonite and palygorskite in composite suspension liquid
Combination degree enhancing, to significantly improve the gelling performance of composite suspension liquid.
From Fig. 5,7,9 as can be seen that montmorillonite-palygorskite inorganic gel materials XRD spectrum is without characteristic diffraction peak, in addition
Crystallographic plane diffraction peak of 2 θ at 6.49 °, 8.50 °, 19.8 ° and 61.8 ° disappears.
From Fig. 6,8,10 as can be seen that the increase of the amount with addition dilute sulfuric acid, montmorillonite-palygorskite inorganic gel materials
The enhancing of the combination degree of middle sheet montmorillonite and rodlike palygorskite forms the network structure that piece-stick mutually supports.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of inorganic gel materials, which is characterized in that the inorganic gel materials include montmorillonite and palygorskite.
2. inorganic gel materials according to claim 1, which is characterized in that montmorillonite and slope in the inorganic gel materials
The mass ratio of thread stone is 1:9~9:1, preferably 6:4~9:1, more preferably 7:3~9:1.
3. inorganic gel materials according to claim 1 or 2, which is characterized in that
The partial size of the montmorillonite is more than 200 mesh, and the partial size of the palygorskite is more than 200 mesh.
4. according to claim 1 to inorganic gel materials described in one of 3, which is characterized in that
The apparent viscosity of the inorganic gel materials be 1150mPa/s or more, preferably 1200mPa/s or more, most preferably
1250mPa/s；The absolute value of the surface Zeta potential of the inorganic gel materials is in 15mV or more, more preferably in 18mV or more, most
It is preferred that in 20mV or more.
5. according to claim 1 to inorganic gel materials described in one of 4, which is characterized in that
The inorganic gel materials further include acids electrolyte,
Preferably, the acids electrolyte is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid.
6. a kind of method for preparing inorganic gel materials according to one of claims 1 to 5, which is characterized in that the side
Method the following steps are included:
Step 1 prepares montmorillonite and palygorskite respectively；
Step 2 mixes montmorillonite and palygorskite with water, obtains suspension；
Step 2 gained suspension is carried out aging process by step 3.
7. preparation method according to claim 6, which is characterized in that
In step 2, the solid content of the suspension is 2%~10%, preferably 4%~8%, more preferably 4%~6%,
The mixed mode is stirring, and the speed of stirring is 10000~15000r/min, preferably 10000~13000r/
Min, more preferably 11000r/min, and
The time of stirring be 10~40min, preferably 15~30min, more preferably 18~25min,
In step 3, the temperature of the aging process is 15~35 DEG C, preferably 20~30 DEG C, such as 25 DEG C of room temperature,
The time of the aging process is 10~30h, preferably 12~20h, more preferably 16h.
8. preparation method according to claim 6 or 7, which is characterized in that the method also includes: acids is added in step 4
Electrolyte,
The acids electrolyte is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and citric acid.
9. preparation method according to claim 8, which is characterized in that after acids electrolyte is added, the Zeta potential of system
For 10~25mV, preferably 17~21mV, more preferably 20~21mV.
10. inorganic gel materials according to one of claims 1 to 5, the preferably side as described in one of claim 6 to 9
Method is made.
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