CN110508256A - One kind having adsorption selectivity composition silicate and preparation method thereof - Google Patents
One kind having adsorption selectivity composition silicate and preparation method thereof Download PDFInfo
- Publication number
- CN110508256A CN110508256A CN201910767961.8A CN201910767961A CN110508256A CN 110508256 A CN110508256 A CN 110508256A CN 201910767961 A CN201910767961 A CN 201910767961A CN 110508256 A CN110508256 A CN 110508256A
- Authority
- CN
- China
- Prior art keywords
- preparation
- adsorption selectivity
- composition silicate
- siliceous materials
- modified
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, the following steps are included: 1) modified first porosity bigger serface siliceous materials, modified second porosity bigger serface siliceous materials and chain extender, methacrylate copolymer are dehydrated recombination reaction under conditions of 90-140 DEG C, react 0.5-3 hours；2) coupling agent is added, carries out coupling recombination reaction, reacts 0.5-2 hours.The present invention is dehydrated recombination reaction under conditions of 90-140 DEG C using modified first porosity bigger serface siliceous materials, modified second porosity bigger serface siliceous materials and chain extender, methacrylate copolymer, and coupling agent coupling recombination reaction is added, its molecular chain length that composition silicate is made, dispersion performance in water is good, absorption property is strong, will not be dissolved in water, and HLB value is high, organic impurities can be effectively adsorbed, Selective adsorption is good；Have many advantages, such as simultaneously degradable and non-toxic.
Description
Technical field
The present invention relates to silicate material water treatment fields, and in particular to one kind has adsorption selectivity composition silicate
And preparation method thereof.
Background technique
Currently, bentonitic main mineral constituent is montmorillonite, bentonite clay particle is by hundreds of single montmorillonite
Cell configuration elementary layer stacking forms, acting through high speed shear and can delaminate as single montmorillonite structure cell in hydrone；Naturally
Montmorillonite structure cell be mingled with alumina octahedral there are two oxygen-octahedron and constitute, in usual rock-steady structure alumina octahedral
Aluminium atom is formed by Mg, Ca, K, Na, Li et al. atomic substitutions and is lacked cationic crystal phase structure body；Therefore, small size band cationic charge
Particle is able to enter montmorillonite structure cell interlayer, and montmorillonite structure cell end face, which externally shows permanent elecrtonegativity, (can adsorb positively charged grain
Son), structure cell surface is externally shown permanent elecrtonegativity (can adsorb negatively charged particle), and such structure feature of montmorillonite determines to cover de-
Stone cation exchange capacity with higher and good adsorption selectivity.Conventional waste water handles adsorbent, such as graphene, work
Property more suction enclosure materials such as charcoal, flyash, zeolite, diatomite, it is such as expensive, two in the application there is respective deficiency
It is secondary to pollute, is low etc. without Selective adsorption, adsorption efficiency.China's bentonite ore reserves are big, and source is very extensive, environment-friendly high-efficiency
And it is cheap；Therefore, exploitation montmorillonite composition silicate Wastewater processing absorbent has very high feasibility.In recent years, state
It is inside and outside more and more extensive in the application study in terms of purification of water quality and wastewater treatment in relation to bentonite, with Selective adsorption
Montmorillonite composite material becomes an ideal chose for replacing conventional waste water processing material.But montmorillonite conduct is used alone
Adsorbent, adsorption range and adsorption capacity all have biggish limitation, and dosage is big to generate a large amount of activated sludge and dehydration difficulty
Greatly.It is all made of and bentonite is modified to promote montmorillonite absorption property on the market at present, but the framework list of its montmorillonite
One, have the defects that bad dispersibility (being not easily stripped as unimolecule structure cell), adsorption effect is weak, dosage is big.
The Chinese invention patent document of Publication No. CN104140149B discloses a kind of modified magnesia unslacked/bentonite water of acid
Treatment agent preparation method, the ratio for 1.5-2:1 (g/g) weighs a certain amount of magnesia unslacked and bentonite in mass ratio, and presses
The technical hydrochloric acid that mass fraction is 9% is added into magnesia unslacked and bentonite for the ratio that mass volume ratio is 1:1.2 (g/mL),
450C-550 DEG C is stirred acidification 30min, arrest reaction 30min, and crushing after microwave or high temperature drying is the acid prepared
Modified magnesia unslacked/bentonite water treatment agent product.Its framework is single, haves the defects that bad dispersibility, adsorption effect are weak.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation side with adsorption selectivity and extra specific surface area silicate
Method is compounded to form specific organo-mineral complexing configuration by coupling, has easy dispersion, extra specific surface area, abundant has
It the features such as selective absorption duct, solves that existing montmorillonite framework is single, lacks there are bad dispersibility, adsorption effect are weak
It falls into.
To achieve the above object, the present invention adopts the following technical scheme that realization:
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by modified multi-pore channel and A kind siliceous materials with Selective adsorption and large specific surface area, modified
Super large specific surface and hydrophobicity transformation after multi-pore channel B kind siliceous materials and chain extender, coupling agent, wetting defoaming dispersing agent it is more
Function additive, acrylate copolymer react under conditions ofs specific temperature, pH value etc., generate a kind of specific organic and inorganic compound
Condensation material；
2) coupling agent is added, carries out coupling recombination reaction, reacts 0.5-2 hours.The present invention uses modified A silicic acid material
Material, modified B siliceous materials and chain extender, acrylic acid esters co-polymer are dehydrated copolyreaction under conditions of 90-140 DEG C,
And coupling agent coupling recombination reaction is added, the molecular chain length of composition silicate is made, dispersion performance in water is good and does not have
There is water imbibition, specific HLB value is strong to organic matter, heavy metal, charged colloidal particles absorption property, and Selective adsorption is good；Simultaneously
Has many advantages, such as degradable and nonhazardous.
The modified A silicic acid mineral material, after purifying modified and in specific acid item under specific alkaline condition
It reacts and is made with the displacement of certain cationic organic matter under part.The present invention is using specific alkali modification agent and PH stabilizer to A silicic acid
Material is modified, and can be effectively removed lixiviating solubility impurity, can significantly increase interlamellar spacing after acting on by alkali, is increased
The monovalent cations such as its low price cation exchange capacity such as Li+, Na+, H+；It can be greatly lowered by acid treatment process
The acid-solubility impurity of A silicic acid mineral material, seeing below organic cation quaternary ammonium salt in specific acid condition can be by inorganic low price
Cation exchanges such as Li+, Na+, H+ cation.
Optionally, the porosity bigger serface silicic acid mineral material includes swelling great soil group clay mine.
Optionally, the A siliceous materials the preparation method comprises the following steps: the alkali that A siliceous materials and mass percent are 2-4.5% changes
Property agent, by pH buffer control pH in 8-10, under conditions of 60-80 DEG C, be stirred to react 1-3 hours；By two to three times
Washing washes out the ionic impurity generated after alkali soluble and extra modifying agent, concentrated obtained refining.
Optionally, the pH buffer includes tris, borate buffer solution and diethylamine buffering
Liquid.The present invention uses tris, borate buffer solution and diethylamine buffer, can efficiently control A silicon
Stabilization pH value in the preparation process of sour material.
Optionally, the preparation method of the A siliceous materials further include: by refining obtained and aluminon or azoviolet, acid
Reagent, specific organic cation season (uncle) salt react 2-3 hours under conditions of 80-90 DEG C, are obtained by washing concentrating dense
Refining after contracting.The present invention is modified A siliceous materials using alkali modification agent, can be effectively removed in A siliceous materials
Alkali solubility impurity increases its cation exchange capacity.
Optionally, the preparation method of the A siliceous materials further include: by the refining after concentration under stable acid condition
Modified by quaternary intercalator, season (uncle) salt form intercalator includes organic quaternary ammonium, quaternary alkylphosphonium salt, quaternary amine salt crust
One of glycan, quaternary amine salt form carbohydrate are a variety of.
Optionally, the modified B siliceous materials are made using B silicic acid mineral by modifier modification, the modification
Agent includes that multipotency group chelating agent, pyrophosphate silane, titanium-containing chelate object are one or more.
Optionally, the B siliceous materials include sepiolite, attapulgite clay.
Optionally, wherein step 1) is additionally added acetylenic diols defoaming, dispersing agent wetting multifunctional assistant.
Optionally, chain extender includes polymer-type chain extender, dimethythiotoluene diamine, 2, in 2 dihydromethyl propionic acids
It is one or more of.
The invention also discloses one kind to have adsorption selectivity organo-mineral complexing silicate, uses above-mentioned preparation side
Method is made.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is total using modified A siliceous materials, modified B siliceous materials and chain extender, methacrylate
Polymers is dehydrated recombination reaction under conditions of 90-140 DEG C, and coupling agent coupling recombination reaction is added, and composition silicate is made
Molecular chain length, dispersion performance in water is good, and adsorption selectivity is strong, and space duct does not absorb water, and can efficiently adsorb useless
Organic impurities and chelating heavy metal ion in water；Has many advantages, such as degradable and nonhazardous simultaneously.
Detailed description of the invention
Fig. 1 is the crystal structure of the sepiolite in the present invention；
Fig. 2 is the process flow chart of the embodiment 1 in the present invention；
Fig. 3 is the infrared light map figure with adsorption selectivity composition silicate of the embodiment 1 in the present invention；
Fig. 4 is the infrared light map figure with adsorption selectivity composition silicate of the embodiment 2 in the present invention；
Fig. 5 is the infrared light map figure with adsorption selectivity composition silicate of the embodiment 3 in the present invention.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this
Invention is further elaborated.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention,
The range being not intended to restrict the invention.In addition, in the following description, descriptions of well-known structures and technologies are omitted, to keep away
Exempt from unnecessarily to obscure idea of the invention.
Part of the invention refers both to parts by weight.
Bentonitic main component of the invention is Montmorillonite Crystal, and the structural configuration of Montmorillonite Crystal is referring to " mineralogy
Report " 2011 years the 1st phases (in March, 2011) of volume 31 " molecular simulation of Montmorillonite Crystal structural configuration and its XRD IR " text
It offers, article number is 1000-4734 (2011) 01-0133-06.
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by modified A siliceous materials, modified B siliceous materials and chain extender, methacrylate copolymer and
Acetylenic diols wetting dispersing agent is dehydrated recombination reaction under conditions of 90-140 DEG C, reacts 0.5-3 hours, obtains primary synthesis and produces
Object；
2) coupling agent is added in primary synthetic product, carries out coupling recombination reaction, react 0.5-2 hours.
Wherein, chain extender includes polymer-type chain extender, dimethythiotoluene diamine, 2, and one in 2 dihydromethyl propionic acids
Kind is several.The polymerization of BASF model Joncryl ADR-4468/4370 can be used in polymer-type chain extender of the invention
Object type chain extender.
Wherein, A siliceous materials use bentonite；B siliceous materials use sepiolite.
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch；Period bentonite raw ore is without broken, drying, milling operation, the direct slurrying of raw ore, with following
Advantage: 1) the former money exploited contains 15% moisture, is easy to meet water dispersion (being not easy to unite) in pulping process, it is de- to fast implement illiteracy
Stone is rapidly and efficiently separated with impurity such as sandstones, 2) former money can guarantee raw ore impurity original state without milling to greatest extent, miscellaneous
Matter is difficult high-efficient simple separation after grinding.
(2) 2-4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, aluminium is added in PH=8-10
Reagent/azoviolet, is heated to 60-80 DEG C, is then stirred to react 1-3 hours；It is concentrated after repeatedly washing and refining is made.
Refining obtained and aluminon or azoviolet, acid reagent are reacted 2-3 hours under conditions of 80-90 DEG C, repeatedly
It is concentrated after washing and refining is made.
It should be noted that alkali modification agent includes: sodium carbonate, lithium carbonate, potassium carbonate, sodium chloride, one in sodium hydroxide
Kind is a variety of.
It should be noted that pH buffer includes that tris, borate buffer solution and diethylamine are slow
Fliud flushing.Here can by PH buffer by PH stability contorting within 8-10, avoid PH from crossing senior general's montmorillonite structure cell superficial silicon dioxide
Silicon dissolution, causes its structural permanent destruction；Avoid PH is too low from can not completely removing the siliceous class impurity such as christobalite, product purity
It is low.
It should be noted that azoviolet includes that magnesium carbonate, magnesia, magnesium hydroxide, magnesium stearate etc. are one or more；Aluminium
Reagent includes that aluminium hydroxide, aluminium chloride, Aluminate, amino acid aluminium etc. are one or more.
Acid reagent includes that the inorganic acids such as the inorganic acids such as hydrochloric acid, sulfuric acid or acetic acid, citric acid, oxalic acid (it is miscellaneous to remove carbonate
Matter), it is not only used to neutralize residual alkali after front end base reagent acts on and removes acid-soluble inorganic salt impurities, but also be organic cation quaternary salt
It creates good ion exchange reaction and creates reaction condition.
Reaction mechanism: montmorillonite belongs to the swollen inorganic gel materials of alkali soluble, and interlamellar spacing can significantly increase after being acted on by alkali
Greatly, interlayer easily enters a large amount of cation such as Li+, Na+, H+, that is, increases its replaceable cation capacity；
(3) PH=3-6 will be adjusted in the refining after concentration, is warming up to 60-90 DEG C, add specific organic quaternary salts type intercalation
Agent is stirred to react 2-4 hours；Repeatedly washed, be concentrated after dry and be milled；Fine powder is made.
Wherein quaternary ammonium salts agent includes the sun such as organic quaternary ammonium salt/quaternary alkylphosphonium salt/Quaternary Ammonium Salt of Chitosan/cation plant polyose
One of modifying ion surface agent is a variety of.
Cation replacement mechanism: cationic organic quaternary salts can cement out the inorganic cation of its interlayer.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
Alcohol reagent mechanism: alcoholic extract hydroxyl group can activate montmorillonite surface silicon atoms to form a large amount of Si-OH ¨ HO-R structures, and alcohol is again
Surface Si-O ¨ H-O-H can be removed, and (silicon atom and water form hydrogen bond, and the steric effect of hydrone is unfavorable at the alkylation of surface
Reason)
On the one hand this can be improved adsorption capacity between montmorillonite layer, and can be in montmorillonite surface grafting functional activity official
It can roll into a ball, can be improved to organic matter selective adsorption capacity.It is contemplated that active function groups HLB value come adjust improve after material choosing
Select adsorptivity and hydrophilic/lipophilic.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
It should be noted that sepiolite soil raw ore, without broken, drying, milling operation, the direct slurrying of raw ore, advantage exists
In: 1) the former money exploited contain 15%-20% moisture, is easy to meet water dispersion (being not easy to unite) in pulping process, can fast implement
Sepiolite is rapidly and efficiently separated with impurity such as sandstones, 2) raw ore can guarantee raw ore impurity initial shape without milling to greatest extent
State, impurity are difficult high-efficient simple separation after grinding.
(2) 2-4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, in the condition of PH=8-10
Lower addition aluminon/azoviolet, is heated to 60-80 DEG C, is then stirred to react 1-3 hours；Then it is washed, is made after concentration
Refining.
Then acid reagent is added in the refining of washing to react 2-3 hours under conditions of 80-90 DEG C, after washing concentrating
Refining；Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 0.5-2 hours, obtained under conditions of 80-100 DEG C
Reaction solution be cooled to room temperature, be added modifying agent, be warming up to 160 DEG C, stir to get modified sepiolite composite material.
It should be noted that the modifying agent include multipotency group chelating agent, pyrophosphate silane, titanium-containing chelate object it is a kind of or
It is a variety of.
Embodiment 1
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by 40 parts of modified bentonite composite material, 5 parts of 60 parts of modified sepiolite composite material and chain extender,
3 parts and 2 parts of acetylenic diols wetting dispersing agent of methacrylate copolymer are dehydrated recombination reaction, reaction 0.5 under conditions of 9 DEG C
Hour；
2) 3 parts of coupling agent are added, coupling recombination reaction is carried out, is reacted 0.5 hour.
Wherein, chain extender includes polymer-type chain extender and dimethythiotoluene diamine, and the weight of both is
1:1 parts.
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch.
(2) 2% (mass percent) alkali modification agent and pH buffer is added in thick slurry, aluminon/magnesium is added in PH=8
Reagent, is heated to 60 DEG C, is then stirred to react 1 hour；Coarse particles are made in washing concentrating.
Refining obtained is reacted 2-3 hours under conditions of 80 DEG C with aluminon or azoviolet, hydrochloric acid, washing concentrating system
Obtain refining.
Wherein, alkali modification agent includes: sodium carbonate, lithium carbonate.
Wherein, pH buffer includes tris, borate buffer solution and diethylamine buffer.
Wherein, azoviolet includes magnesium carbonate, magnesia；Aluminon includes aluminium hydroxide.
(3) Quaternary Ammonium Salt of Chitosan and hydrated cation intercalator will be added in the refining after concentration, is modified；It is reacted
After dry and be milled；Fine powder is made.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
(2) 2% (mass percent) alkali modification agent and pH buffer is added in thick slurry, is added under conditions of PH=8
Aluminon/azoviolet, is heated to 60 DEG C, is then stirred to react 1 hour；Then it is washed, the refining after washing is made.
Then acid reagent is added in the refining of washing to react 2 hours under conditions of 80 DEG C, the refining after being concentrated；
Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 0.5 hour, obtained reaction under conditions of 80 DEG C
Liquid is cooled to room temperature, and pyrophosphate silane, titanium-containing chelate object is added, is warming up to 160 DEG C, and it is multiple to stir to get modified sepiolite
Condensation material.
It is obtained in the present invention that there is adsorption selectivity composition silicate, infrared spectrogram such as Fig. 3 institute of detection
Show.
Embodiment 2
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by 50 parts of modified bentonite composite material, 5 parts of 50 parts of modified sepiolite composite material and chain extender,
3 parts of methacrylate copolymer and acetylenic diols wetting dispersing agent are dehydrated recombination reaction, reaction 1.5 under conditions of 115 DEG C
Hour；
2) 1.5 parts of coupling agent are added, coupling recombination reaction is carried out, is reacted 1 hour.
Wherein, chain extender includes polymer-type chain extender and dimethythiotoluene diamine, and the weight of both is
2:1。
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch.
(2) 2-4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, PH9 be added aluminon/
Azoviolet, is heated to 70 DEG C, is then stirred to react 2 hours；Refining is made in washing concentrating.
Refining obtained is reacted 2.5 hours under conditions of 85 DEG C with aluminon or azoviolet, hydrochloric acid, washing concentrating system
Obtain refining.
Wherein, alkali modification agent includes: sodium carbonate, lithium carbonate.
Wherein, pH buffer includes tris, borate buffer solution and diethylamine buffer.
Wherein, azoviolet includes magnesium carbonate, magnesia；Aluminon includes aluminium hydroxide.
(3) Quaternary Ammonium Salt of Chitosan and hydrated cation intercalator will be added in the refining after concentration, is modified；It is reacted
After dry and be milled；Fine powder is made.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
(2) 2-4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, under conditions of PH=9
Aluminon/azoviolet is added, is heated to 70 DEG C, is then stirred to react 2 hours；Then it is washed, the refining after washing is made.
Then acid reagent is added in the refining of washing to react 2.5 hours under conditions of 85 DEG C, the essence after being concentrated
Slurry；Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 1 hour, obtained reaction solution under conditions of 90 DEG C
It is cooled to room temperature, pyrophosphate silane, titanium-containing chelate object is added, is warming up to 160 DEG C, it is compound to stir to get modified sepiolite
Material.
It is obtained in the present invention that there is adsorption selectivity composition silicate, infrared spectrogram such as Fig. 4 institute of detection
Show.
Embodiment 3
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by 30 parts of modified bentonite composite material, modified sepiolite composite material and 70 parts of chain extender, first
4 parts of base acrylate copolymer and acetylenic diols wetting dispersing agent are dehydrated recombination reaction under conditions of 140 DEG C, react 3 hours；
2) 2.5 parts of coupling agent are added, coupling recombination reaction is carried out, is reacted 2 hours.
Wherein, chain extender includes polymer-type chain extender and dimethythiotoluene diamine, and the weight of both is
5:4。
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch.
(2) 4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, aluminium examination is added in PH=10
Agent/azoviolet, is heated to 80 DEG C, is then stirred to react 3 hours；Refining is made.
Refining obtained is reacted 3 hours, after being concentrated under conditions of 90 DEG C with aluminon or azoviolet, hydrochloric acid
Refining.
Wherein, alkali modification agent includes: sodium carbonate, lithium carbonate.
Wherein, pH buffer includes tris, borate buffer solution and diethylamine buffer.
Wherein, azoviolet includes magnesium carbonate, magnesia；Aluminon includes aluminium hydroxide.
(3) Quaternary Ammonium Salt of Chitosan and hydrated cation intercalator will be added in the refining after concentration, is modified；It is reacted
After dry and be milled；Fine powder is made.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
(2) 4.5% (mass percent) alkali modification agent and pH buffer is added in thick slurry, adds under conditions of PH=10
Enter aluminon/azoviolet, be heated to 80 DEG C, is then stirred to react 3 hours；Then it is washed, the refining after washing is made.
Then acid reagent is added in the refining of washing to react 3 hours under conditions of 90 DEG C, the refining after being concentrated；
Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 2 hours, obtained reaction under conditions of 100 DEG C
Liquid is cooled to room temperature, and pyrophosphate silane, titanium-containing chelate object is added, is warming up to 160 DEG C, and it is multiple to stir to get modified sepiolite
Condensation material.
It is obtained in the present invention that there is adsorption selectivity composition silicate, infrared spectrogram such as Fig. 5 institute of detection
Show.
Comparative example 1
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by 30 parts of modified bentonite composite material, modified sepiolite composite material and 30 parts of chain extender, first
2 parts and 2 parts of acetylenic diols wetting dispersing agent of base acrylate copolymer are dehydrated recombination reaction, reaction 0.4 under conditions of 89 DEG C
Hour；
2) 5 parts of coupling agent are added, coupling recombination reaction is carried out, is reacted 0.42 hour.
Wherein, chain extender includes polymer-type chain extender and dimethythiotoluene diamine, and the weight of both is
1:5。
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch.
(2) 2% (mass percent) alkali modification agent and pH buffer is added in thick slurry, aluminon/magnesium is added in PH=7
Reagent, is heated to 55 DEG C, is then stirred to react 0.5 hour；Refining is made.
Refining obtained is reacted 1 hour, after being concentrated under conditions of 75 DEG C with aluminon or azoviolet, hydrochloric acid
Refining.
Wherein, alkali modification agent includes: sodium carbonate, lithium carbonate.
Wherein, pH buffer includes tris, borate buffer solution and diethylamine buffer.
Wherein, azoviolet includes magnesium carbonate, magnesia；Aluminon includes aluminium hydroxide.
(3) Quaternary Ammonium Salt of Chitosan and hydrated cation intercalator will be added in the refining after concentration, is modified；It is reacted
After wash, dry and be milled；Fine powder is made.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
(2) 1% (mass percent) alkali modification agent and pH buffer is added in thick slurry, is added under conditions of PH=7
Aluminon/azoviolet, is heated to 55 DEG C, is then stirred to react 0.5 hour；Then it is washed, the refining after washing is made.
Then acid reagent is added in the refining of washing to react 1.5 hours under conditions of 75 DEG C, the essence after being concentrated
Slurry；Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 0.4 hour, obtained reaction under conditions of 75 DEG C
Liquid is cooled to room temperature, and pyrophosphate silane, titanium-containing chelate object is added, is warming up to 160 DEG C, and it is multiple to stir to get modified sepiolite
Condensation material.
Comparative example 2
The present invention provides a kind of preparation methods with adsorption selectivity composition silicate, comprising the following steps:
1) by 25 parts of modified bentonite composite material, modified sepiolite composite material and 75 parts of chain extender, first
5 parts and 1 part of acetylenic diols wetting dispersing agent of base acrylate copolymer part are dehydrated recombination reaction under conditions of 141 DEG C, react
3.5 hour；
2) 5 parts of coupling agent are added, coupling recombination reaction is carried out, is reacted 2.1 hours.
Wherein, chain extender includes polymer-type chain extender and dimethythiotoluene diamine, and the weight of both is
3:2。
Modified bentonite composite material preparation method:
(1) add water to be then concentrated in bentonite raw ore, 20% slurries made are made, then pass through series connection hydrocyclone
Separation is made and slightly will slightly starch.
(2) 4.6% (mass percent) alkali modification agent and pH buffer is added in thick slurry, aluminium examination is added in PH=11
Agent/azoviolet, is heated to 81 DEG C, is then stirred to react 3.5 hours；Thick slurry is made in washing concentrating.
Refining obtained is reacted 3.1 hours, after obtaining concentration under conditions of 95 DEG C with aluminon or azoviolet, hydrochloric acid
Refining.
Wherein, alkali modification agent includes: sodium carbonate, lithium carbonate.
Wherein, pH buffer includes tris, borate buffer solution and diethylamine buffer.
Wherein, azoviolet includes magnesium carbonate, magnesia；Aluminon includes aluminium hydroxide.
(3) Quaternary Ammonium Salt of Chitosan and hydrated cation intercalator will be added in the refining after concentration, is modified；It is reacted
After dry and be milled；Fine powder is made.
(4) alcohol reagent and silicol class coupling agent is added in fine powder obtained, during which carries out heating stirring；Obtain mud
Finished product is made by drying, milling in cake, mud cake.
The preparation of modified sepiolite composite material:
(1) by sepiolite soil raw ore, water is added, then the magma that concentration is 20% is made in concentration, uses 100 mesh vibrating screens
Thick slurry is made then by series connection hydrocyclone slagging-off in filtering.
(2) 4.6% (mass percent) alkali modification agent and pH buffer is added in thick slurry, adds under conditions of PH=11
Enter aluminon/azoviolet, be heated to 82 DEG C, is then stirred to react 3.2 hours；Then it is washed, the refining after washing is made.
Then acid reagent is added in the refining of washing to react 2-3 hours under conditions of 91 DEG C, the essence after being concentrated
Slurry；Refining after concentration is washed, filter-press dehydration again, finally dried and be milled, purification sepiolite powder is made；
(3) fine powder obtained addition alcohol reagent is stirred and is reacted 2.5 hours, what is obtained is anti-under conditions of 105 DEG C
It answers liquid to be cooled to room temperature, pyrophosphate silane, titanium-containing chelate object is added, is warming up to 160 DEG C, stirs to get modified sepiolite
Composite material.
The embodiment of the present invention 1, embodiment 2, embodiment 3, the testing adsorption effect method and inspection of comparative example 1 and comparative example 2
Survey effect:
1, certain automobile parts factory waste water is taken
Composition silicate adsorbent configuration 5% is contained into concentrate admittedly, waste water pH value sodium hydroxide is modulated into 8-9 additional amount
It puts into, is sufficiently stirred by wastewater flow rate 2%, after standing 2 hours, clear liquid is taken to test；
2, electrophoresis is taken to clean waste water
Composition silicate adsorbent configuration 5% is contained into concentrate admittedly, waste water pH value sodium hydroxide is modulated into 8-9 additional amount
It puts into, is sufficiently stirred by wastewater flow rate 2%, after standing 2 hours, clear liquid is taken to test.
3, painting wastewater is taken
Composition silicate adsorbent configuration 5% is contained into concentrate admittedly, waste water pH value sodium hydroxide is modulated into 8-9 additional amount
It puts into, is sufficiently stirred by wastewater flow rate 2%, after standing 2 hours, clear liquid is taken to test.
4, electrophoresis rinse bath waste water is taken
Composition silicate adsorbent configuration 5% is contained into concentrate admittedly, waste water pH value sodium hydroxide is modulated into 8-9 additional amount
It puts into, is sufficiently stirred by wastewater flow rate 2%, after standing 2 hours, clear liquid is taken to test.
5, degreasing is inclined slot waste water
Composition silicate adsorbent configuration 5% is contained into concentrate admittedly, waste water pH value sodium hydroxide is modulated into 8-9 additional amount
It puts into, is sufficiently stirred by wastewater flow rate 2%, after standing 2 hours, clear liquid is taken to test.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (12)
1. a kind of preparation method with adsorption selectivity composition silicate, which comprises the following steps:
1) by modified A siliceous materials, modified B siliceous materials and chain extender, methacrylate copolymer in 90-
It is dehydrated recombination reaction under conditions of 140 DEG C, reacts 0.5-3 hours；
2) coupling agent is added, carries out coupling recombination reaction, reacts 0.5-2 hours.
2. as described in claim 1 with the preparation method of adsorption selectivity composition silicate, which is characterized in that described to change
Property after A silicate material using A silicic acid raw ore by react obtained with alkali modification agent under alkaline condition.
3. as described in claim 1 with the preparation method of adsorption selectivity composition silicate, which is characterized in that described more
Permeability bigger serface siliceous materials include bentonite.
4. as claimed in claim 2 with the preparation method of adsorption selectivity composition silicate, which is characterized in that the A
Siliceous materials the preparation method comprises the following steps: A siliceous materials and mass percent are the alkali modification agent of 2-4.5%, in 60-80 DEG C of condition
Under, and pH is controlled in 8-10 by pH buffer, it is stirred to react 1-3 hours obtained refinings.
5. as claimed in claim 4 with the preparation method of adsorption selectivity composition silicate, which is characterized in that the pH
Buffer includes tris, borate buffer solution and diethylamine buffer.
6. as claimed in claim 4 with the preparation method of adsorption selectivity composition silicate, which is characterized in that the A
The preparation method of siliceous materials further include: by refining obtained and aluminon or azoviolet, acid reagent under conditions of 80-90 DEG C
Reaction 2-3 hours, the refining after being concentrated.
7. as claimed in claim 5 with the preparation method of adsorption selectivity composition silicate, which is characterized in that the A
The preparation method of siliceous materials further include: be modified the refining after concentration by quaternary intercalator, quaternary intercalation
Agent includes one or more of organic quaternary ammonium salt, quaternary alkylphosphonium salt, Quaternary Ammonium Salt of Chitosan.
8. the preparation method with adsorption selectivity composition silicate as described in claim 1 to 7, which is characterized in that institute
It states modified B siliceous materials and is made using B siliceous materials by modifier modification, the modifying agent includes multipotency group chelating
Agent, pyrophosphate silane, titanium-containing chelate object are one or more.
9. as claimed in claim 8 with the preparation method of adsorption selectivity composition silicate, which is characterized in that the B
Siliceous materials include sepiolite.
10. the preparation method with adsorption selectivity composition silicate as described in claim 1 to 7, which is characterized in that its
Middle step 1) is additionally added acetylenic diols wetting dispersing agent.
11. the preparation method with adsorption selectivity composition silicate as described in claim 1 to 7, which is characterized in that institute
Stating chain extender includes one of polymer-type chain extender, dimethythiotoluene diamine, 2,2 dihydromethyl propionic acids or a variety of.
12. one kind has adsorption selectivity composition silicate, which is characterized in that described that there is adsorption selectivity complex silicate
Preparation method described in claim of the salt using 1 to 11 any one with adsorption selectivity composition silicate is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910767961.8A CN110508256A (en) | 2019-08-20 | 2019-08-20 | One kind having adsorption selectivity composition silicate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910767961.8A CN110508256A (en) | 2019-08-20 | 2019-08-20 | One kind having adsorption selectivity composition silicate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110508256A true CN110508256A (en) | 2019-11-29 |
Family
ID=68625840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910767961.8A Pending CN110508256A (en) | 2019-08-20 | 2019-08-20 | One kind having adsorption selectivity composition silicate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110508256A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254199A (en) * | 2022-07-11 | 2022-11-01 | 山东工业陶瓷研究设计院有限公司 | Low-cost denitration catalyst slurry and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100275664A1 (en) * | 2007-11-08 | 2010-11-04 | Volker Windhoevel | Soil improver and use thereof |
| CN102631898A (en) * | 2012-04-26 | 2012-08-15 | 西北师范大学 | Preparation of bentonite-based copolymer and use of bentonite-based copolymer as adsorbent |
| CN104353436A (en) * | 2014-11-05 | 2015-02-18 | 朱忠良 | Method for preparing modified bentonite for removing sulfide in fume |
| CN104609526A (en) * | 2014-12-29 | 2015-05-13 | 许昌学院 | Heavy metal collector and preparation method thereof |
| CN105289542A (en) * | 2015-11-13 | 2016-02-03 | 无锡清杨机械制造有限公司 | Preparation method of bentonite with hydrophilic modification |
| CN106582583A (en) * | 2016-12-14 | 2017-04-26 | 严帝 | Polymethyl methacrylate modified attapulgite adsorbent and preparation method thereof |
| CN108083357A (en) * | 2017-12-29 | 2018-05-29 | 安徽阳城化工科技有限公司 | One kind removes mould water treatment composite material |
-
2019
- 2019-08-20 CN CN201910767961.8A patent/CN110508256A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100275664A1 (en) * | 2007-11-08 | 2010-11-04 | Volker Windhoevel | Soil improver and use thereof |
| CN102631898A (en) * | 2012-04-26 | 2012-08-15 | 西北师范大学 | Preparation of bentonite-based copolymer and use of bentonite-based copolymer as adsorbent |
| CN104353436A (en) * | 2014-11-05 | 2015-02-18 | 朱忠良 | Method for preparing modified bentonite for removing sulfide in fume |
| CN104609526A (en) * | 2014-12-29 | 2015-05-13 | 许昌学院 | Heavy metal collector and preparation method thereof |
| CN105289542A (en) * | 2015-11-13 | 2016-02-03 | 无锡清杨机械制造有限公司 | Preparation method of bentonite with hydrophilic modification |
| CN106582583A (en) * | 2016-12-14 | 2017-04-26 | 严帝 | Polymethyl methacrylate modified attapulgite adsorbent and preparation method thereof |
| CN108083357A (en) * | 2017-12-29 | 2018-05-29 | 安徽阳城化工科技有限公司 | One kind removes mould water treatment composite material |
Non-Patent Citations (1)
| Title |
|---|
| 郑水林等: "《粉体表面改性（第四版）》", 30 June 2019, 中国建材工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254199A (en) * | 2022-07-11 | 2022-11-01 | 山东工业陶瓷研究设计院有限公司 | Low-cost denitration catalyst slurry and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104291349B (en) | A kind of take flyash as the method that P type molecular sieve prepared by raw material | |
| Chunfeng et al. | Evaluation of zeolites synthesized from fly ash as potential adsorbents for wastewater containing heavy metals | |
| CN102516607B (en) | Preparation method of magnetic rectorite/chitosan nano-grade composite material | |
| Dhillon et al. | Recent advances and spectroscopic perspectives in fluoride removal | |
| CN1803294A (en) | Alkaline calcium bentonite and its preparation method | |
| CN105289562B (en) | Heavy metal wastewater thereby recoverying and utilizing method | |
| CN103638744B (en) | A kind of method improving acid flyash slurry filtration performance | |
| CN102249255A (en) | Anionic-nonionic composite organic montmorillonite and preparation method thereof | |
| CN106378119B (en) | A kind of preparation method of La-Fe/CTMAB composite modified bentonite adsorbent material | |
| Ren et al. | Extraction and preparation of metal organic frameworks from secondary aluminum ash for removal mechanism study of fluoride in wastewater | |
| CN101033231B (en) | Method of preparing high-purity medical xanthonumic acid | |
| CN106179521A (en) | A kind of preparation method of the magnetic attapulgite clay of loaded composite photocatalysis agent | |
| CN105597666B (en) | A kind of oil shale semi-coke processing and attapulgite modified method | |
| CN106943995A (en) | A kind of modified clinoptilolite and preparation method and remove waste water in Pb ions application | |
| CN112076727A (en) | Heavy metal pollution repairing agent and preparation method thereof | |
| CN113387394A (en) | Preparation method of layered double-metal hydroxide material based on biobased calcium carbonate | |
| Lei et al. | An improved implementable process for the synthesis of zeolite 4A from bauxite tailings and its Cr 3+ removal capacity | |
| CN103936023B (en) | A kind of preparation method of calcium ion selective molecular sieve and scale removal application thereof | |
| CN110508256A (en) | One kind having adsorption selectivity composition silicate and preparation method thereof | |
| CN109502679B (en) | Method for preparing flocculating agent and porous material by synergistic utilization of multiple elements of fly ash | |
| CN101007635A (en) | Organic-pillared vermiculite mesoporous material and its preparing process and uses | |
| CN108654703A (en) | A kind of preparation method of Gemini surface active agent pillared modification montmorillonite | |
| CN105084398B (en) | A kind of method of asbestos tailings comprehensive utilization | |
| CN102989426A (en) | Hydrothermal liquid phase preparation method of magnetic kaolinite/chitosan composite | |
| CN101734678A (en) | Organic modified bentonite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191129 |