CN106540652B - A kind of quaternary ammonium salt cationic is modified flying dust and preparation method thereof - Google Patents
A kind of quaternary ammonium salt cationic is modified flying dust and preparation method thereof Download PDFInfo
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- CN106540652B CN106540652B CN201610871039.XA CN201610871039A CN106540652B CN 106540652 B CN106540652 B CN 106540652B CN 201610871039 A CN201610871039 A CN 201610871039A CN 106540652 B CN106540652 B CN 106540652B
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- flying dust
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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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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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
-
- 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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of quaternary ammonium salt cationics to be modified flying dust adsorbent, 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%；It weighs the amino silicane coupling agent solution of above-mentioned preparation, flying dust is added, after being stirred at room temperature 30-60 minute, filtering, filter cake cools down 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, it is spare to obtain aminosilane coupling agent modifying flying dust；The aminosilane coupling agent modifying flying dust of preparation and cationic reagent are subjected to nitrogen alkylation reaction, quaternary ammonium salt cationic is prepared and is modified flying dust adsorbent.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 quaternary ammonium salt cationic of the present invention is modified the more former flying dust of flying dust compares.
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 be modified flying dust adsorbent 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.Flying dust is also known as flyash, is the waste of coal-burning power plant pulverized coal friring discharge, primary chemical at
It is divided into silicon, aluminium, the oxide of iron and a certain amount of calcium, magnesium, oxysulfide, wherein silica, aluminium oxide, iron oxide gross mass
Account for about the 85% of flying dust gross mass.Flying dust is a kind of porosity bulk solids aggregation, and porosity is generally 60%-75%, has
A large amount of microcellular structure and larger specific surface area, and derive from a wealth of sources, cheap, adsorption capacity is strong, therefore at waste water
It can be used as adsorbent when reason and flocculant use.However flying dust itself is weaker to the Dye Adsorption ability in dyeing waste water, inhales
Attached decoloring 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 flying dust, has the characteristics that good filter-aid performance, exploitation are a kind of to dye
Expect that there is stronger adsorption bleaching ability with dyestuff in printing and dyeing industrial waste water and the quaternary ammonium salt cationic that fixed bed needs can be met to change
Property flying dust adsorbent and preparation method thereof.
Invention content
A kind of quaternary ammonium salt cationic modification flying dust, 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,
Flying dust is added, after being stirred at room temperature 30-60 minute, filtering, filter cake after dry 1-3 hours, is done at 50-60 DEG C then at 120 DEG C of constant temperature
Dry reaction 1-2 hours, cooling, it is spare to obtain aminosilane coupling agent modifying flying dust；Obtained aminosilane coupling agent modifying is flown
Ash adds in the water of 4-6 times of flying dust quality, with lye pH adjustment=9-11.Stirring is warming up to 40-70 DEG C, controls pH=9-11, protects
Under the conditions of temperature, cationic etherifying reagent solution is added dropwise while stirring, continues to stir insulation reaction 1-2 hours after adding, tune pH=
6.5-7 is filtered, and washing is less than 80 DEG C of dryings, is obtained quaternary ammonium salt cationic and is modified flying dust；Alcohol solution described above is methanol
Solution or ethanol solution；Silane coupling agent described above is 3- aminopropanes triethoxysilane or 3- aminopropane front threes
Oxysilane or 3- aminopropanes-methyldiethoxysilane；Flying dust described above, SiO2、Al2O3And Fe2O3Quality contains
Amount is more than the 80% of flying dust gross mass, porosity 60%-75%, and grain size is 1-300 μm；Cationic etherifying reagent described above
For 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides or 2,3- epoxypropyltrimethylchloride chlorides.
The technical characterstic and excellent results of the present invention：
Quaternary ammonium salt cationic prepared by the present invention, which is modified flying dust, 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, flying dust in the prior art can be overcome
The relatively poor defect of adsorption bleaching characteristic.It is modified flying dust with quaternary ammonium salt cationic prepared by the present invention, using absorption method to dye
Material 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
The preparation of silane coupler modified flying dust：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 40 grams of flying dusts, 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 constant temperature
Dry reaction 1 hour, cooling, obtains silane coupler modified flying dust.
Embodiment 2
Quaternary ammonium salt cationic is modified the preparation of flying dust adsorbent A：In the four-hole boiling flask of the 250ml equipped with reflux condenser
In, 80ml deionized waters are added, silane coupler modified flying dust prepared by 20 grams of embodiments 1 is added, are 10% with mass concentration
Sodium hydroxide solution tune pH=9.5-10, stirring are warming up to 50 DEG C, control pH=9.5-10, under 50 DEG C of heat-retaining conditions, while stirring
The 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride solution that 18 gram mass percentage concentrations are 50% is added dropwise, it is anti-to continue stirring heat preservation after adding
It answers 90 minutes, adjusts pH=6.5-7, filter, wash, it is dry at 80 DEG C, it obtains quaternary ammonium salt cationic and is modified flying dust adsorbent A.
Embodiment 3
Adsorption bleaching characteristic is tested：Respectively using 20g flying dusts, 20g quaternary ammonium salt cationics modification flying dust adsorbent as adsorbent,
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）It carries out
Column chromatography records colourless chromatography liquid product, and 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 be modified flying dust adsorbent A it is obviously high to the adsorption bleaching ability of organic dyestuff
In the adsorption bleaching ability of flying dust.
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 quaternary ammonium salt cationic is modified the preparation method of flying dust, 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, flying dust is added, after being stirred at room temperature 30-60 minute, filter, filter cake is at 50-60 DEG C after dry 1-3 hours, then at 120
DEG C freeze-day with constant temperature reacts 1-2 hour, cools down, it is spare to obtain aminosilane coupling agent modifying flying dust；Obtained amino silane is coupled
Agent is modified flying dust and adds in the water of 4-6 times of flying dust quality, and 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, washing is less than 80 DEG C of dryings, obtains quaternary ammonium salt cationic and is modified flying dust；Alcohol solution described above is
Methanol solution or ethanol solution；Silane coupling agent described above is 3- aminopropanes triethoxysilane or 3- aminopropanes
Trimethoxy silane or 3- aminopropanes-methyldiethoxysilane；Flying dust described above, SiO2、Al2O3And Fe2O3Matter
Content is more than flying dust gross mass 80% is measured, porosity 60%-75%, grain size is 1-300 μm；Cation etherificate described above
Reagent is 3- chloro-2-hydroxypropyl-trimethyl ammonium chlorides or 2,3- epoxypropyltrimethylchloride chlorides.
2. a kind of quaternary ammonium salt cationic is modified flying dust adsorbent, it is characterised in that prepared according to preparation method described in claim 1
And it obtains.
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| CN107511140A (en) * | 2017-10-09 | 2017-12-26 | 常州建轩纺织品有限公司 | A kind of preparation method of high dephosphorization amount diatomite adsorbing material |
| CN110655137B (en) * | 2019-08-23 | 2020-06-23 | 中国矿业大学 | Fly ash-based high-salinity organic wastewater purification and biomass catalytic pyrolysis combined treatment process |
| CN113893828A (en) * | 2021-11-23 | 2022-01-07 | 华东理工大学 | Preparation method of porous electropositive fly ash adsorbent |
| CN115717276B (en) * | 2022-11-30 | 2023-07-21 | 芯安健康科技(广东)有限公司 | Far infrared antibacterial, anti-mite and antiviral multifunctional fiber and mattress protection pad |
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| CN101574639A (en) * | 2008-05-07 | 2009-11-11 | 山西大同大学 | Hydrosulphonyl silane/modified fly ash adsorbent as well as preparation method and application thereof |
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| CN103071465A (en) * | 2013-01-14 | 2013-05-01 | 杜亚丽 | Preparation method of spherical polymerized micron-size flyash particles |
| CN103521198A (en) * | 2013-10-15 | 2014-01-22 | 杭州电子科技大学 | Preparation method of heavy rare earth ion imprinting molecular sieve selective adsorbent |
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