CN106334529B - A kind of quaternary ammonium salt cationic type diatomite and preparation method thereof - Google Patents
A kind of quaternary ammonium salt cationic type diatomite and preparation method thereof Download PDFInfo
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- CN106334529B CN106334529B CN201610871040.2A CN201610871040A CN106334529B CN 106334529 B CN106334529 B CN 106334529B CN 201610871040 A CN201610871040 A CN 201610871040A CN 106334529 B CN106334529 B CN 106334529B
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- diatomite
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- ammonium salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of quaternary ammonium salt cationic type diatomite adsorbants, it is characterised in that is prepared as follows：In the alcoholic solution that mass concentration is 90%, while amino silicane coupling agent is slowly added dropwise, while with acetic acid tune pH=3-4, after dripping off, continues that stirring is transparent to solution, obtain the amino silicane coupling agent solution for standby that mass fraction is 0.1%-3%；The amino silicane coupling agent solution of above-mentioned preparation is weighed, diatomite is added, after being stirred at room temperature 30-60 minutes, filtering, filter cake is at 50-60 DEG C after dry 1-3 hours, then in 120 DEG C of freeze-day with constant temperature reactions 1-2 hours, cooling, it is spare to obtain aminosilane coupling agent modifying diatomite；The aminosilane coupling agent modifying diatomite of preparation and cationic reagent are subjected to nitrogen alkylation reaction, prepare quaternary ammonium salt cationic type diatomite adsorbant.Adsorption bleaching can significantly improve the removal rate of organic dyestuff in dyestuff and printing and dyeing industrial waste water it is demonstrated experimentally that a kind of more former diatomite of quaternary ammonium salt cationic type diatomite of the present invention is compared.
Description
Technical field
The present invention relates to a kind of cation adsorbing materials, are handled for dyestuff and printing and dyeing industrial waste water more particularly to one kind
Quaternary ammonium salt cationic type diatomite adsorbant and preparation method thereof.
Background technology
The annual output of whole world organic dyestuff is up to more than 70 ten thousand tons, wherein about 12% dyestuff is in production and application process
In be discharged in a manner of colorful wastewater.Due to waste water from dyestuff complicated components, coloration is deep and COD and BOD values are relatively high,
Direct emission will necessarily cause seriously to pollute to environment, therefore need to carry out wastewater treatment before discharging.Common dyes waste water
Processing method includes mainly flocculence, oxidizing process, bioanalysis, absorption method etc., wherein the sludge quantity that flocculence generates is big and is dehydrated
Difficulty, Treatment of Sludge operating cost is high, and be easy to cause secondary pollution；Oxidizing process energy consumption is larger, and COD removal rates are relatively low；Biology
Method has certain requirement to conditions such as pH, the temperature of waste water from dyestuff, it is difficult to adapt to that variation water quality is big, dyes is more, toxicity is high
Waste water from dyestuff；Absorption method has equipment investment and floor space relatively fewer, the easy to operate and excellent feature of decolorizing effect.
In absorption method, common adsorbent is mainly activated carbon and ion exchange resin.Activated carbon is as a kind of excellent adsorbent
It is early widely used in water process, is still the best adsorbent of colored dyes waste water so far, however due to expensive, because
This is generally only applied to the lower dye wastewater treatment of concentration；Ion exchange resin has stronger adsorption energy to dye molecule
Power, but cause cost for wastewater treatment higher since regeneration is difficult, and then limit its popularization in dye wastewater treatment and answer
With, therefore a kind of adsorbent that absorption property is excellent, cheap of development is always that dyestuff and printing and dyeing industrial waste water are handled
The hot subject of research field.Diatomite is a kind of biogenic siliceous sedimentary rock, is made of ancient times diatom remains, chemistry
Ingredient is mainly SiO2, contain a small amount of Al2O3、Fe2O3、CaO、MgO、K2O、Na2O、P2O5And organic matter.Diatomite has big
The microcellular structure of amount and larger specific surface area, cheap, derive from a wealth of sources, drainage effect is good, and has certain adsorption energy
Power, therefore often it is used as adsorbent and the use of sludge filter aid in wastewater treatment.However diatomite itself is in dyeing waste water
Dye Adsorption ability is weaker, and adsorption bleaching ability is difficult to the actual needs for meeting dyeing waste water to performance of the adsorbent.
The purpose of the present invention is cheap and easy to get aiming at diatomite, has the characteristics that good filter-aid performance, exploitation are a kind of right
Dyestuff has stronger adsorption bleaching ability with dyestuff in printing and dyeing industrial waste water and can meet the quaternary ammonium salt cationic of fixed bed needs
Type diatomite adsorbant and preparation method thereof.
Invention content
A kind of quaternary ammonium salt cationic type diatomite, it is characterised in that implement as follows：The alcohol for being 90% in mass concentration
In aqueous solution, while amino silicane coupling agent is slowly added dropwise, while with acetic acid tune pH=3-4, after dripping off, it is transparent to solution to continue stirring,
Obtain the amino silicane coupling agent solution for standby that mass fraction is 0.1%-3%；The amino silicane coupling agent solution of above-mentioned preparation is weighed,
Diatomite is added, after being stirred at room temperature 30-60 minute, filters, filter cake is at 50-60 DEG C after dry 1-3 hours, then at 120 DEG C of constant temperature
Dry reaction 1-2 hours, cooling, it is spare to obtain aminosilane coupling agent modifying diatomite；Obtained amino silicane coupling agent is changed
Property diatomite adds in the water of 4-6 times of diatomite quality, with lye pH adjustment=9-11.Stirring is warming up to 40-70 DEG C, and control pH=
9-11 under heat-retaining condition, is added dropwise cationic etherifying reagent solution, continues to stir insulation reaction 1-2 hours after adding while stirring,
PH=6.5-7 is adjusted, is filtered, is washed, it is dry at 80 DEG C, obtain quaternary ammonium salt cationic type diatomite；Alcohol solution described above is first
Alcoholic solution or ethanol solution；Silane coupling agent described above is 3- aminopropanes triethoxysilane or 3- aminopropanes three
Methoxy silane or 3- aminopropanes-methyldiethoxysilane；Its SiO of diatomite described above2Content >=75%, Fe2O3
≤ 3%, loss on ignition≤10%, the mesh of mesh number >=80；Cationic etherifying reagent described above is the chloro- 2- Hydroxyproyl Trimethyls chlorinations of 3-
Ammonium or 2,3- epoxypropyltrimethylchloride chlorides.
The technical characterstic and excellent results of the present invention：
Quaternary ammonium salt cationic type diatomite prepared by the present invention can not only utilize the micro-porous adsorption of its own to decolourize, simultaneously
Anionic pollutant in its surface cation positive charge adsorbing and removing waste water can also be utilized, diatom in the prior art can be overcome
The relatively poor defect of native adsorption bleaching characteristic.With quaternary ammonium salt cationic type diatomite prepared by the present invention, using absorption method pair
Dyestuff is handled with printing and dyeing industrial waste water, compared with strong-base anion-exchange resin, can be substantially reduced operating cost.
It is further illustrated the present invention below by specific example.
Specific implementation mode
Embodiment 1
Silane coupler modified diatomaceous preparation：The ethyl alcohol for weighing 190 gram masses a concentration of 90%, with acetic acid tune pH=3-
3.5,2 grams of silane coupling agent 3- aminopropane triethoxysilanes are slowly added dropwise at pH=3-3.5, after dripping off, continue to stir
30-60 minutes transparent to solution, adds the ethyl alcohol that mass concentration is 90%, until 200 grams of total amount, obtains the amino that mass fraction is 1%
Silane coupler solution is spare；100 grams of amino silicane coupling agent solution for weighing above-mentioned preparation is put into 250ml beakers, then is added
Enter 50 grams of diatomite, after being stirred at room temperature 30 minutes, filtering, after filter cake is dried in vacuo 2 hours at 50 DEG C, then at 120 DEG C of normal pressure perseverances
Warm dry reaction 1 hour, cooling, obtains silane coupler modified diatomite.
Embodiment 2
The preparation of quaternary ammonium salt cationic modification infusorial earth adsorbent A：In the four-hole boiling flask of the 250mL equipped with reflux condenser
In, 80mL deionized waters are added, aminosilane coupling agent modifying diatomite prepared by 20 grams of embodiments 1 is added, uses mass concentration
For 10% sodium hydroxide solution tune pH=9.5-10, stirring is warming up to 50 DEG C, controls pH=9.5-10, under 50 DEG C of heat-retaining conditions, side
It stirs side and the 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution that 18 gram mass percentage concentrations are 50% is added dropwise, continue to stir after adding
Insulation reaction 90 minutes adjusts pH=6.5-7, filters, washing, dry at 80 DEG C, obtains quaternary ammonium salt cationic and is modified flying dust adsorbent
A。
Embodiment 3
Adsorption bleaching characteristic is tested：It is respectively to inhale with 20g diatomite, 20g quaternary ammonium salt cationic modification infusorial earth adsorbents
Attached dose, using dry column-packing, the thin layer chromatography column of a diameter of 20mm is prepared, at room temperature to dye wastewater（500 mg/L）
Column chromatography is carried out, records colourless chromatography liquid product, the results are shown in Table 1.
The comparison of different adsorbent adsorption capacities in 1 column chromatography adsorption experiment of table
Table 1 statistics indicate that, quaternary ammonium salt cationic modification infusorial earth adsorbent A is apparent to the adsorption bleaching ability of organic dyestuff
Higher than diatomaceous adsorption bleaching ability.
Certainly, above description is not limitation of the present invention, and the present invention is also not limited to the example above, the art
Those of ordinary skill, the present invention essential scope in, variation, addition or the replacement made, should all belong to the present invention guarantor
Protect range.
Claims (2)
1. a kind of diatomaceous preparation method of quaternary ammonium salt cationic type, it is characterised in that implement as follows：In mass concentration
In 90% alcohol solution, while amino silicane coupling agent is slowly added dropwise, while with acetic acid tune pH=3-4, after dripping off, to continue stirring extremely
Solution is transparent, obtains the amino silicane coupling agent solution for standby that mass fraction is 0.1%-3%；The amino silane for weighing above-mentioned preparation is even
Join agent solution, diatomite be added, after being stirred at room temperature 30-60 minute, filter, filter cake at 50-60 DEG C after dry 1-3 hours, then at
120 DEG C of freeze-day with constant temperature react 1-2 hours, and it is spare to obtain aminosilane coupling agent modifying diatomite for cooling；The amino silane that will be obtained
Coupling agent modified diatomite adds in the water of 4-6 times of diatomite quality, and with lye pH adjustment=9-11, stirring is warming up to 40-70
DEG C, pH=9-11 is controlled, under heat-retaining condition, cationic etherifying reagent solution is added dropwise while stirring, it is anti-to continue stirring heat preservation after adding
It answers 1-2 hours, adjusts pH=6.5-7, filter, wash, it is dry at 80 DEG C, obtain quaternary ammonium salt cationic type diatomite；Alcohol described above
Aqueous solution is methanol solution or ethanol solution；Silane coupling agent described above is 3- aminopropanes triethoxysilane or 3-
Aminopropane trimethoxy silane or 3- aminopropanes-methyldiethoxysilane；Its SiO of diatomite described above2Content
>=75%, Fe2O3≤ 3%, loss on ignition≤10%, the mesh of mesh number >=80；Cationic etherifying reagent described above is the chloro- 2- hydroxypropyls of 3-
Trimethyl ammonium chloride or 2,3- epoxypropyltrimethylchloride chlorides.
2. a kind of quaternary ammonium salt cationic type diatomite adsorbant, it is characterised in that prepared according to preparation method described in claim 1
And it obtains.
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