CN106732395A - Modified attapulgite clay adsorbent of a kind of alkyl guanidine and preparation method thereof - Google Patents

Modified attapulgite clay adsorbent of a kind of alkyl guanidine and preparation method thereof Download PDF

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Publication number
CN106732395A
CN106732395A CN201611152179.8A CN201611152179A CN106732395A CN 106732395 A CN106732395 A CN 106732395A CN 201611152179 A CN201611152179 A CN 201611152179A CN 106732395 A CN106732395 A CN 106732395A
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parts
temperature
attapulgite
attapulgite clay
alkyl guanidine
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严帝
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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
    • B01J20/12—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
    • B01J20/02—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
    • 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
    • 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
    • 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
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The modified attapulgite clay adsorbent of a kind of alkyl guanidine, it is characterised in that it is prepared from by following raw material：100 parts of concave convex rod original soil, 600 800 parts of sodium chloride solution, 12 15 parts of na-montmorillonite, 15 20 parts of cetylamine, 8 10 parts of AminoiminomethanesulAcidc Acidc, 600 800 parts of absolute ethyl alcohol, 70 80 parts of methyl methacrylate, 30 40 parts of dimethyl silicone polymer, 34 parts of azodiisobutyronitrile, 8 10 parts of tert-butyl catechol, 500 600 parts of acetone, 600 800 parts of methyl alcohol, appropriate deionized water.Present invention process is simple and does not produce secondary pollution, and prepared attapulgite clay adsorbent has big particle diameter, free settling, easily reclaim and the characteristics of absorption property is good, it is adaptable to Industrial Wastewater Treatment.

Description

Modified attapulgite clay adsorbent of a kind of alkyl guanidine and preparation method thereof
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of alkyl guanidine modified attapulgite clay adsorbent and its system Preparation Method.
Background technology
Industrial wastewater causes human body and the great potential safety hazard of animals and plants to the pollution that water body, soil are brought, and how to have The harm that effect ground eliminates heavy metal is the outstanding problem that current efforts at environmental protection face.In recent years, sorbing material with high because adsorbing The advantages of efficiency, easily regeneration, adsorption process are exothermic reaction, is widely used in heavy metal ion pollution control.
Attapulgite has the advantages that cheap raw material, aboundresources and specific surface area are big as a kind of natural material, concavo-convex Rod soil has special fibre structure and crystal structure, is allowed to, with many special materializations and processing performance, there is " thousand soil King " and the good reputation of " soil of general-purpose ".Because attapulgite has larger specific surface area, stronger suction-operated is made it have, High-viscosity suspension can be formed under at a fairly low concentration, its rheological property determines that it can be used as dytory, suspends Agent, thixotropic agent and binding agent, but attapulgite powder there is a problem of being difficult to precipitate in water, easily causes secondary pollution. Improvement attapulgite property is paid close attention to by those skilled in the art.
Author Yin Jingzhou et al. exists《The absorption of Heavy Metal Ions on Attapulgite Modified by Chitosan》In one text, with concave convex rod Soil is carrier, by chitosan loaded in attapulgite's surface, then is chelated with heavy metal ion.The adsorbent can both save shitosan Addition, makes lock out operation simple and easy to apply again, has the advantages that the rate of adsorption is fast, adsorption capacity is big, pollution-free.
The content of the invention
Present invention aim at modified attapulgite clay adsorbent of a kind of alkyl guanidine of offer and preparation method thereof.
To achieve these goals, the technical solution adopted by the present invention is as follows：
The modified attapulgite clay adsorbent of a kind of alkyl guanidine, it is characterised in that it is prepared from by the raw material of following weight portion：It is recessed 100 parts of convex rod original soil, sodium chloride solution 600-800 parts, na-montmorillonite 12-15 parts, cetylamine 15-20 parts, AminoiminomethanesulAcidc Acidc 8-10 parts, absolute ethyl alcohol 600-800 parts, methyl methacrylate 70-80 parts, dimethyl silicone polymer 30-40 parts, azo two it is different Butyronitrile 3-4 parts, tert-butyl catechol 8-10 parts, acetone 500-600 parts, methyl alcohol 600-800 parts, appropriate deionized water.
The modified attapulgite clay adsorbent of described alkyl guanidine, it is characterised in that it is prepared from by following steps：
（1）Concave convex rod original soil is sieved by 200 mesh sieve, is washed with deionized 3-5 times, remove the impurity of remaining, then used Sodium chloride solution is washed 2-3 times, and moisture removal is removed in drying；The attapulgite and na-montmorillonite that will have been washed are mixed Compound, after being raised to 250 DEG C from room temperature, by inert gas N2Make vapor and mixture haptoreaction as carrier gas, further High-temperature is risen to 320-350 DEG C, after keeping 2-3h, starts cooling, and stop adding vapor, after temperature is down to room temperature, taken Go out, the attapulgite for being pre-processed；
（2）The attapulgite of pretreatment is added to 1/3 absolute ethyl alcohol and the deionized water equivalent to absolute ethyl alcohol weight portion In the solution of configuration, ultrasonic disperse 2-3h rises high-temperature to 50-60 DEG C of addition cetylamine and continues constant temperature stirring, every 0.5h points Three addition AminoiminomethanesulAcidc Acidcs, addition stops stirring, naturally cools to room temperature, takes out after finishing continuation constant temperature stirring reaction 2-3h Filter, is washed with deionized to neutrality, then with remaining absolute ethanol washing 2-3 times, dries naturally；
（3）By step（2）Product, methyl methacrylate, dimethyl silicone polymer, 1/3 azodiisobutyronitrile add dress Have in the reactor of reflux condensate device, be sufficiently stirred for being well mixed reactant；Oil bath heating heats up, and controlling reaction temperature is 80-90 DEG C, after stirring reaction 3-5h under the rotating speed of 300-500r/min, add remaining azodiisobutyronitrile and tert-butyl o Benzenediol, rises high-temperature to 140-150 DEG C, continues agitating heating 8-10h；Room temperature is cooled to, acetone is added, continues to stir 1- 2h, adds methyl alcohol, and standing sedimentation 8-10h, filtering, 60-80 DEG C of vacuum drying 10-12h obtains the modified concave convex rod of alkyl guanidine Earth adsorbing.
The modified attapulgite clay adsorbent of described alkyl guanidine, it is characterised in that described concentration of sodium chloride solution is 2- 3mol/L。
The beneficial effects of the invention are as follows：The present invention carries out removal of impurities pretreatment to concave convex rod original soil and uses water vapour pair first Attapulgite carries out activation process, the cavitation for recycling ultrasonic wave to cause, the shock wave and microjet for being formed in the solution The strong mutual collision between attapulgite aggregation can be caused, the aggregation of the rod crystalline substance beam of attapulgite or brilliant beam is beaten It is broken, nano-attapulgite suspension is prepared so as to reach, increase the cation exchange capacity of attapulgite, suppress attapulgite certainly The phenomenon that body is reunited；The alkyl guanidine of strong basicity, high stability, preferable bioactivity and hypotoxicity is recycled to its surface grafting Modification, the attapulgite clay adsorbent of polymethyl methacrylate cladding is prepared using the method for in-situ polymerization, by attapulgite Rigidity, the toughness of dimensional stability and heat endurance and polymethyl methacrylate, machinability and dielectricity ideally tie Altogether, heavy metal cation not only in absorption trade effluent, moreover it is possible to adsorb Organic Pollution, process organic wastewater；This hair It is bright to also added na-montmorillonite, also add the adsorption capacity and heat-resistant stability of adsorbent.Present invention process is simply and not Secondary pollution is produced, prepared attapulgite clay adsorbent has big particle diameter, free settling, easily reclaims and the good spy of absorption property Point, it is adaptable to Industrial Wastewater Treatment.
Specific embodiment
The modified attapulgite clay adsorbent of the alkyl guanidine of the present embodiment, it is prepared from by the raw material of following weight portion：It is recessed 100 parts of convex rod original soil, 800 parts of sodium chloride solution, 15 parts of na-montmorillonite, 20 parts of cetylamine, 10 parts of AminoiminomethanesulAcidc Acidc, anhydrous second 800 parts of alcohol, 80 parts of methyl methacrylate, 40 parts of dimethyl silicone polymer, 4 parts of azodiisobutyronitrile, tert-butyl catechol 10 parts, 600 parts of acetone, 800 parts of methyl alcohol, appropriate deionized water.
The modified attapulgite clay adsorbent of the alkyl guanidine of the present embodiment, it is prepared from by following steps：
（1）Concave convex rod original soil is sieved by 200 mesh sieve, is washed with deionized 5 times, remove the impurity of remaining, then use chlorine Change sodium solution to wash 3 times, moisture removal is removed in drying；The attapulgite and na-montmorillonite that will have been washed are mixed Thing, after being raised to 250 DEG C from room temperature, by inert gas N2Make vapor and mixture haptoreaction as carrier gas, further rise High-temperature after keeping 3h, starts cooling to 350 DEG C, and stops adding vapor, after temperature is down to room temperature, takes out, and obtains pre- The attapulgite for the treatment of；
（2）The attapulgite of pretreatment is added to 1/3 absolute ethyl alcohol and the deionized water equivalent to absolute ethyl alcohol weight portion In the solution of configuration, ultrasonic disperse 3h rises high-temperature to 60 DEG C of addition cetylamines and continues constant temperature stirring, adds in three times every 0.5h Enter AminoiminomethanesulAcidc Acidc, addition stops stirring after finishing continuation constant temperature stirring reaction 3h, naturally cool to room temperature, suction filtration, spend from Sub- water washing is dried naturally to neutrality, then with remaining absolute ethanol washing 3 times；
（3）By step（2）Product, methyl methacrylate, dimethyl silicone polymer, 1/3 azodiisobutyronitrile add dress Have in the reactor of reflux condensate device, be sufficiently stirred for being well mixed reactant；Oil bath heating heats up, and controlling reaction temperature is 90 DEG C, after stirring reaction 5h under the rotating speed of 500r/min, remaining azodiisobutyronitrile and tert-butyl catechol are added, risen High-temperature continues agitating heating 10h to 150 DEG C；Room temperature is cooled to, acetone is added, continues to stir 2h, add methyl alcohol, stood Sedimentation 10h, filtering, 80 DEG C of vacuum drying 12h obtain the modified attapulgite clay adsorbent of alkyl guanidine.
It is that 20mg/L contains Cu respectively to concentration with the attapulgite clay adsorbent obtained by the present embodiment2+、Cd2+、Pb2+It is useless Water carries out adsorption treatment, the speed of agitator for 1g/L, 250r/min and absorption in the granular concave rod earth adsorbing dosage Time be 2h under conditions of, Cu in waste water2+、Cd2+、Pb2+Clearance be all higher than 90%.

Claims (3)

1. the attapulgite clay adsorbent that a kind of alkyl guanidine is modified, it is characterised in that it is prepared from by the raw material of following weight portion： 100 parts of concave convex rod original soil, sodium chloride solution 600-800 parts, na-montmorillonite 12-15 parts, cetylamine 15-20 parts, sulfur trioxide Urea 8-10 parts, absolute ethyl alcohol 600-800 parts, methyl methacrylate 70-80 parts, dimethyl silicone polymer 30-40 parts, azo two Isobutyronitrile 3-4 parts, tert-butyl catechol 8-10 parts, acetone 500-600 parts, methyl alcohol 600-800 parts, appropriate deionized water.
2. the modified attapulgite clay adsorbent of alkyl guanidine according to claims 1, it is characterised in that it is by following steps It is prepared from：
（1）Concave convex rod original soil is sieved by 200 mesh sieve, is washed with deionized 3-5 times, remove the impurity of remaining, then used Sodium chloride solution is washed 2-3 times, and moisture removal is removed in drying；The attapulgite and na-montmorillonite that will have been washed are mixed Compound, after being raised to 250 DEG C from room temperature, by inert gas N2Make vapor and mixture haptoreaction as carrier gas, further High-temperature is risen to 320-350 DEG C, after keeping 2-3h, starts cooling, and stop adding vapor, after temperature is down to room temperature, taken Go out, the attapulgite for being pre-processed；
（2）The attapulgite of pretreatment is added to 1/3 absolute ethyl alcohol and the deionized water equivalent to absolute ethyl alcohol weight portion In the solution of configuration, ultrasonic disperse 2-3h rises high-temperature to 50-60 DEG C of addition cetylamine and continues constant temperature stirring, every 0.5h points Three addition AminoiminomethanesulAcidc Acidcs, addition stops stirring, naturally cools to room temperature, takes out after finishing continuation constant temperature stirring reaction 2-3h Filter, is washed with deionized to neutrality, then with remaining absolute ethanol washing 2-3 times, dries naturally；
（3）By step（2）Product, methyl methacrylate, dimethyl silicone polymer, 1/3 azodiisobutyronitrile add dress Have in the reactor of reflux condensate device, be sufficiently stirred for being well mixed reactant；Oil bath heating heats up, and controlling reaction temperature is 80-90 DEG C, after stirring reaction 3-5h under the rotating speed of 300-500r/min, add remaining azodiisobutyronitrile and tert-butyl o Benzenediol, rises high-temperature to 140-150 DEG C, continues agitating heating 8-10h；Room temperature is cooled to, acetone is added, continues to stir 1- 2h, adds methyl alcohol, and standing sedimentation 8-10h, filtering, 60-80 DEG C of vacuum drying 10-12h obtains the modified concave convex rod of alkyl guanidine Earth adsorbing.
3. the modified attapulgite clay adsorbent of alkyl guanidine according to claims 1,2, it is characterised in that described chlorination Sodium solution concentration is 2-3mol/L.
CN201611152179.8A 2016-12-14 2016-12-14 Modified attapulgite clay adsorbent of a kind of alkyl guanidine and preparation method thereof Withdrawn CN106732395A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538047A (en) * 2009-04-29 2009-09-23 淮阴师范学院 Method for preparing long-chain alkylguanidine-modified attapulgite
CN102977256A (en) * 2012-12-05 2013-03-20 淮阴师范学院 Acrylic ester-attapulgite composite oil-absorbing material and preparation method thereof
CN103012699A (en) * 2012-12-05 2013-04-03 常州大学 Attapulgite grafted polymethyl methacrylate hybrid particle and preparation method thereof
CN103894143A (en) * 2014-03-18 2014-07-02 苏州宇希新材料科技有限公司 Method for activating attapulgite
CN104275161A (en) * 2014-11-07 2015-01-14 中国科学院兰州化学物理研究所 Granular cationic dye adsorbent and preparation method thereof
CN106000356A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538047A (en) * 2009-04-29 2009-09-23 淮阴师范学院 Method for preparing long-chain alkylguanidine-modified attapulgite
CN102977256A (en) * 2012-12-05 2013-03-20 淮阴师范学院 Acrylic ester-attapulgite composite oil-absorbing material and preparation method thereof
CN103012699A (en) * 2012-12-05 2013-04-03 常州大学 Attapulgite grafted polymethyl methacrylate hybrid particle and preparation method thereof
CN103894143A (en) * 2014-03-18 2014-07-02 苏州宇希新材料科技有限公司 Method for activating attapulgite
CN104275161A (en) * 2014-11-07 2015-01-14 中国科学院兰州化学物理研究所 Granular cationic dye adsorbent and preparation method thereof
CN106000356A (en) * 2016-06-16 2016-10-12 江苏麦阁吸附剂有限公司 Attapulgite/polyacrylic acid compound heavy metal absorbent and preparation method thereof

Non-Patent Citations (1)

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Title
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