CN106669619A - Lignin modified attapulgite clay adsorbent and preparation method thereof - Google Patents
Lignin modified attapulgite clay adsorbent and preparation method thereof Download PDFInfo
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- CN106669619A CN106669619A CN201611153569.7A CN201611153569A CN106669619A CN 106669619 A CN106669619 A CN 106669619A CN 201611153569 A CN201611153569 A CN 201611153569A CN 106669619 A CN106669619 A CN 106669619A
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- attapulgite
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a lignin modified attapulgite clay adsorbent, which is characterized by being prepared from the following raw materials: attapulgite raw clay, a sodium chloride solution, nano calcium carbonate, acetic acid lignin, propargyl bromide, a sodium hydroxide solution, tetrahydrofuran, 3-mercapto-1,2,4-triazole, 2,2-dimethoxy-2-phenylacetophenone, methyl methacrylate, phenyltrimethoxysilane, azodiisobutyronitrile, 3-mercaptopropionic acid, acetone, methanol, an appropriate amount of hydrochloric acid, an appropriate amount of absolute ethyl alcohol and an appropriate amount of deionized water. The preparation method is simple in process; the secondary pollution is not generated; the prepared attapulgite clay adsorbent has the characteristics of being large in particle size, easy to subside, easy to recover and favorable in adsorbability, and is applicable to the treatment of industrial wastewater.
Description
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of attapulgite clay adsorbent and its system of lignin modification
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
Effect ground eliminates the outstanding problem that the harm of heavy metal is that current efforts at environmental protection face.In recent years, adsorbing material is because with high absorption
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 so as to stronger adsorption,
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 attapulgite
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 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 providing a kind of attapulgite clay adsorbent of lignin modification and preparation method thereof.
To achieve these goals, the technical solution used in the present invention is as follows：
A kind of attapulgite clay adsorbent of lignin modification, 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, nano-calcium carbonate 12-15 parts, acetic acid lignin 15-20 parts, propargyl bromide
15-20 parts, sodium hydroxide solution 600-800 parts, tetrahydrofuran 500-600 parts, 3- sulfydryl -1,2,4- triazole 6-8 parts, 2,2- bis-
Methoxyl group -2- phenyl acetophenone 8-10 parts, methyl methacrylate 70-80 parts, phenyltrimethoxysila,e 30-40 part, azo
Bis-isobutyronitrile 3-4 parts, 3- mercaptopropionic acid 8-10 parts, acetone 500-600 parts, methanol 600-800 parts, appropriate hydrochloric acid, dehydrated alcohol
In right amount, appropriate deionized water.
The attapulgite clay adsorbent of described lignin modification, it is characterised in that it is prepared from by following steps：
（1）Attapulgite original soil is sieved through 200 mesh sieve, is washed with deionized 3-5 time, remove the impurity of remaining, then used
Sodium chloride solution is washed 2-3 time, and moisture removal is removed in drying；The attapulgite for having washed and nano-calcium carbonate mix homogeneously are mixed
Compound, after being raised to 250 DEG C from room temperature, by noble gases N2Vapor and mixture haptoreaction are made 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, obtain the attapulgite of pretreatment；
（2）Acetic acid lignin is dissolved in into sodium hydroxide solution, propargyl bromide is added, at 70-80 DEG C 3-4h is reacted, be subsequently cooled to room
Temperature, with hydrochloric acid conditioning solution pH to 2-3, separates out yellow solid, filters, and is respectively washed 2-3 time with dehydrated alcohol, deionized water, does
It is dry；By dried product and step（1）The pretreated attapulgite for obtaining is added in tetrahydrofuran, ultrasonic disperse 2-
3h, adds 3- sulfydryl -1,2,4- triazoles and 2,2- dimethoxy -2- phenyl acetophenones, in the ultra violet lamp that wavelength is 365nm
Lower reaction 20-30min, after reaction, vacuum distillation removes tetrahydrofuran, and system Jing dehydrated alcohol and deionized water respectively wash 2-3
It is secondary, vacuum lyophilization；
（3）By step（2）Product, methyl methacrylate, phenyltrimethoxysila,e, 1/3 azodiisobutyronitrile add
In reactor equipped with reflux condensate device, it is sufficiently stirred for making reactant mix homogeneously；Oil bath heating heats up, controlling reaction temperature
For 80-90 DEG C, after stirring reaction 3-5h under the rotating speed of 300-500r/min, remaining azodiisobutyronitrile and 3- sulfydryls are added
Propanoic acid, 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,
Methanol is added, standing sedimentation 8-10h is filtered, 60-80 DEG C of vacuum drying 10-12h obtains the attapulgite of lignin modification
Adsorbent.
The attapulgite clay adsorbent of described lignin modification, it is characterised in that described concentration of sodium chloride solution is 2-
3mol/L, the sodium hydroxide solution of described hydrochloric acid is 1-2mol/L, and the concentration of described hydrochloric acid is 1-2mol/L.
The invention has the beneficial effects as follows：The present invention carries out first remove impurity pretreatment and using water vapour pair to attapulgite original soil
Attapulgite carries out activation processing, the cavitation that recycling ultrasound wave causes, the shock wave for being formed in the solution and microjet
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；Sulfide-containing Hindered knot is prepared using sulfydryl-alkynes type click-reaction in the controllable modification of attapulgite and lignin surface
Structure unit, then using in-situ polymerization method prepare polymethyl methacrylate cladding attapulgite clay adsorbent, will be concavo-convex
The rigid of rod soil, the toughness of dimensional stability and heat stability and polymethyl methacrylate, machinability and dielectricity are perfect
Ground combines, and not only adsorbs the heavy metal cation in trade effluent, moreover it is possible to adsorb Organic Pollution；The addition of lignin with
Attapulgite synergism, imparts the heavy metal ion adsorption selectivity and higher adsorption capacity of adsorbent；This
Bright process is simple and secondary pollution is not produced, prepared attapulgite clay adsorbent has big particle diameter, free settling, easily reclaims and inhale
Attached functional the characteristics of, it is adaptable to Industrial Wastewater Treatment.
Specific embodiment
The attapulgite clay adsorbent of the lignin modification 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 nano-calcium carbonate, 20 parts of acetic acid lignin, 20 parts of propargyl bromide, hydroxide
800 parts of sodium solution, 600 parts of tetrahydrofuran, 8 parts of 3- sulfydryl -1,2,4- triazoles, 10 parts of 2,2- dimethoxy -2- phenyl acetophenones,
80 parts of methyl methacrylate, 30 parts of phenyltrimethoxysila,e, 4 parts of azodiisobutyronitrile, 10 parts of 3- mercaptopropionic acids, acetone
600 parts, 800 parts of methanol, appropriate hydrochloric acid, appropriate dehydrated alcohol, appropriate deionized water.
The attapulgite clay adsorbent of the lignin modification of the present embodiment, it is prepared from by following steps：
（1）Attapulgite original soil is sieved through 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 for having washed and nano-calcium carbonate mix homogeneously are mixed
Thing, after being raised to 250 DEG C from room temperature, by noble gases N2Vapor and mixture haptoreaction are made as carrier gas, is further risen
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 of process；
（2）Acetic acid lignin is dissolved in into sodium hydroxide solution, propargyl bromide is added, at 80 DEG C 4h is reacted, be subsequently cooled to room temperature, used
Hydrochloric acid conditioning solution pH to 2-3, separates out yellow solid, filters, and is respectively washed 3 times with dehydrated alcohol, deionized water, is dried；Will be dry
Product and step after dry（1）The pretreated attapulgite for obtaining is added in tetrahydrofuran, ultrasonic disperse 3h, adds 3-
Sulfydryl -1,2,4- triazoles and 2,2- dimethoxy -2- phenyl acetophenones, react in the case where wavelength is for the ultra violet lamp of 365nm
30min, after reaction, vacuum distillation removes tetrahydrofuran, system Jing dehydrated alcohol and deionized water respectively washing 3 times, vacuum freezing
It is dried；
（3）By step（2）Product, methyl methacrylate, phenyltrimethoxysila,e, 1/3 azodiisobutyronitrile add
In reactor equipped with reflux condensate device, it is sufficiently stirred for making reactant mix homogeneously；Oil bath heating heats up, controlling reaction temperature
For 90 DEG C, after stirring reaction 5h under the rotating speed of 500r/min, remaining azodiisobutyronitrile and 3- mercaptopropionic acids are added, raised
Temperature continues agitating heating 10h to 150 DEG C；Room temperature is cooled to, acetone is added, continues to stir 2h, add methanol, it is heavy to stand
Drop 10h, filters, 80 DEG C of vacuum drying 12h, obtains the attapulgite clay adsorbent of lignin modification.
With the attapulgite clay adsorbent obtained by the present embodiment be to concentration 20mg/L respectively contain Cu2+、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 is Cu in waste water under conditions of 2h2+、Cd2+、Pb2+Clearance be all higher than 90%.
Claims (3)
1. a kind of attapulgite clay adsorbent of lignin modification, it is characterised in that it is prepared from by the raw material of following weight portion：
100 parts of attapulgite original soil, sodium chloride solution 600-800 parts, nano-calcium carbonate 12-15 parts, acetic acid lignin 15-20 parts, bromine third
Alkynes 15-20 parts, sodium hydroxide solution 600-800 parts, tetrahydrofuran 500-600 parts, 3- sulfydryl -1,2,4- triazole 6-8 parts, 2,2-
Dimethoxy -2- phenyl acetophenone 8-10 parts, methyl methacrylate 70-80 parts, phenyltrimethoxysila,e 30-40 part, idol
Nitrogen bis-isobutyronitrile 3-4 parts, 3- mercaptopropionic acid 8-10 parts, acetone 500-600 parts, methanol 600-800 parts, appropriate hydrochloric acid, anhydrous second
Appropriate alcohol, appropriate deionized water.
2. the attapulgite clay adsorbent of the lignin modification according to claims 1, it is characterised in that it is by following steps
It is prepared from：
（1）Attapulgite original soil is sieved through 200 mesh sieve, is washed with deionized 3-5 time, remove the impurity of remaining, then used
Sodium chloride solution is washed 2-3 time, and moisture removal is removed in drying；The attapulgite for having washed and nano-calcium carbonate mix homogeneously are mixed
Compound, after being raised to 250 DEG C from room temperature, by noble gases N2Vapor and mixture haptoreaction are made 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, obtain the attapulgite of pretreatment；
（2）Acetic acid lignin is dissolved in into sodium hydroxide solution, propargyl bromide is added, at 70-80 DEG C 3-4h is reacted, be subsequently cooled to room
Temperature, with hydrochloric acid conditioning solution pH to 2-3, separates out yellow solid, filters, and is respectively washed 2-3 time with dehydrated alcohol, deionized water, does
It is dry；By dried product and step（1）The pretreated attapulgite for obtaining is added in tetrahydrofuran, ultrasonic disperse 2-
3h, adds 3- sulfydryl -1,2,4- triazoles and 2,2- dimethoxy -2- phenyl acetophenones, in the ultra violet lamp that wavelength is 365nm
Lower reaction 20-30min, after reaction, vacuum distillation removes tetrahydrofuran, and system Jing dehydrated alcohol and deionized water respectively wash 2-3
It is secondary, vacuum lyophilization；
（3）By step（2）Product, methyl methacrylate, phenyltrimethoxysila,e, 1/3 azodiisobutyronitrile add
In reactor equipped with reflux condensate device, it is sufficiently stirred for making reactant mix homogeneously；Oil bath heating heats up, controlling reaction temperature
For 80-90 DEG C, after stirring reaction 3-5h under the rotating speed of 300-500r/min, remaining azodiisobutyronitrile and 3- sulfydryls are added
Propanoic acid, 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,
Methanol is added, standing sedimentation 8-10h is filtered, 60-80 DEG C of vacuum drying 10-12h obtains the attapulgite of lignin modification
Adsorbent.
3. the attapulgite clay adsorbent of the lignin modification according to claims 1,2, it is characterised in that described chlorination
Sodium solution concentration is 2-3mol/L, and the sodium hydroxide solution of described hydrochloric acid is 1-2mol/L, and the concentration of described hydrochloric acid is 1-
2mol/L。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105126772A (en) * | 2015-08-06 | 2015-12-09 | 中国林业科学研究院林产化学工业研究所 | Lignin-based heavy metal ion adsorbent containing thiol ether structure, 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 |
-
2016
- 2016-12-14 CN CN201611153569.7A patent/CN106669619A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105126772A (en) * | 2015-08-06 | 2015-12-09 | 中国林业科学研究院林产化学工业研究所 | Lignin-based heavy metal ion adsorbent containing thiol ether structure, 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 |
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