CN109400720A - A kind of preparation method and application of amphoteric cellulose adsorbent - Google Patents
A kind of preparation method and application of amphoteric cellulose adsorbent Download PDFInfo
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- CN109400720A CN109400720A CN201811231679.XA CN201811231679A CN109400720A CN 109400720 A CN109400720 A CN 109400720A CN 201811231679 A CN201811231679 A CN 201811231679A CN 109400720 A CN109400720 A CN 109400720A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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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
- B01J20/28023—Fibres or filaments
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/103—Arsenic 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a kind of preparation methods of amphoteric cellulose adsorbent, and cellulose is added in sodium hydroxide-aqueous solution of urea first, obtains cellulose suspension after mixing evenly；Then it thaws, is uniformly mixed again after being freezed, obtain cellulose solution；Cellulose solution is centrifuged, take supernatant, bis- (2- acetate) amine derivative aqueous solutions, bis- (pyridine ethyl) amine derivative aqueous solutions are successively added dropwise into supernatant, after being stirred to react 2-12h at a temperature of 50-100 DEG C, obtain reaction product, reaction product is successively washed with deionized water, acetone, ether, then filter, it is dry to get.What the amphoteric cellulose adsorbent material surface of the method for the present invention preparation connected is the ionic groups of " pincer " structure, this is more than the active group of single-stranded ionic group modified cellulose, suction-operated is stronger, and the method for the present invention reaction step is few, reaction condition is mild, it is easy to operate, it is conducive to large-scale production.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of preparation method of amphoteric cellulose adsorbent and its
Application as water body purification adsorbent material.
Background technique
With the rapid development of sharp increase and the industry of population, water environment pollution has become a serious problem, especially
It is that heavy metal pollution is particularly acute.Since heavy metal ion is difficult to degrade, can accumulate in vivo, can be transmitted by biological chain,
So heavy metal ion pollution has seriously threatened aquatic ecosystem and other biological system and human life's safety.
Absorption method because the advantages that equipment is simple, operating cost is low, high treating effect always wastewater treatment research hot spot,
Therefore, efficient, cheap, environmental-friendly adsorbent is developed to be concerned.Cellulose as a kind of abundance, it is cheap,
Asepsis environment-protecting, good biocompatibility and can be degradable natural material, be used for sewage water process with huge economy
And social value.Since hydrogen bond action is more in cellulosic molecule, cause its absorption property not strong, so many scholars are to fiber
It is modified.Wherein amphoteric cellulose is that a kind of a kind of water cellulose element simultaneously containing cation and anionic group is derivative
Object can simultaneously adsorb negatively charged and positively charged pollutant, and adsorption efficiency is high.This kind of material sewage treatment,
The fields such as oilfield exploitation, daily-use chemical industry have broad application prospects.
About amphoteric cellulose preparation method, there are also the reports of document in recent years, such as: hear seapeak to absorbent cotton according to
It is secondary to be alkalized, carboxy methylation, quaternized obtain amphoteric cellulose；(shaddock ped cellulose prepares both sexes heavy metal ion to Fu Weichang
Remover and its application in Electrolytic Manganese Wastewater processing, Hunan University .2002) with epoxychloropropane, dimethylamine and monoxone
As ionization reagent, cotton fiber and shaddock ped fiber are modified, betaine type amphoteric ion fiber element adsorbent is made；Clock
Pretty (development of wheat straw amphoteric chelate sorbent containing and the Study on adsorption properties [D] to Cu (II) and Cr (VI), Shandong University
.2011) with N, N- dimethyl methyl acid amide is medium, and the amination using wheat straw waste and epoxychloropropane, ethylenediamine, triethylamine is anti-
It answers, obtains cationic wheat straw quaternary amine adsorbent；Then using isopropanol as solvent, monoxone is ionization reagent, and wheat is made
Careless amphoteric ion adsorbent WSAA；Have scholar (Zhang, W., et al., Carbohydrate Polymers.2012 90 (2),
887-893.) using epoxychloropropane, trimethylamine and monoxone be ionization reagent, fiber is modified, be made both sexes from
Subbundle element adsorbent.However the amphoteric cellulose of above-mentioned report, ionic groups are that single-stranded form is linked to fiber
Surface, therefore, the adsorption active site of gained amphoteric fibers cellulosic material is relatively fewer, thus affect to heavy metal from
The removal effect of son.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and applications of amphoteric cellulose adsorbent, to solve the prior art
Ionic group is that amphoteric cellulose caused by the surface of fiber is linked in single-stranded form to the removal effect of heavy metal
The problem of difference.
The principle of the present invention:
The technical solution adopted in the present invention is as follows:
A kind of preparation method of amphoteric cellulose adsorbent, includes the following steps:
(1) cellulose is added in sodium hydroxide-aqueous solution of urea, obtains cellulose suspension after mixing evenly；
(2) it thaws again after freezing the cellulose suspension of step (1), is then uniformly mixed, it is molten to obtain cellulose
Liquid；
(3) cellulose solution of step (2) is centrifuged, takes supernatant, bis- (2- acetate) amine are successively added dropwise into supernatant and spread out
The aqueous solution of biology and the aqueous solution of bis- (pyridine ethyl) amine derivatives obtain after being stirred to react 2-12h at a temperature of 50-100 DEG C
To reaction product, reaction product is successively washed with deionized water, acetone, ether, then filters, is dry, obtained product is i.e.
For amphoteric cellulose adsorbent.
In step (1), the cellulose is microcrystalline cellulose or gossypin.
Further, in step (1), in the sodium hydroxide-aqueous solution of urea, sodium hydroxide, urea, deionized water weight
Amount is than being 20:10:170.
Further, in step (1), speed of agitator 2000rpm, time 10min.
Further, in step (2), cryogenic temperature is -20 DEG C, and the time is for 24 hours.
Further, in step (2), speed of agitator 1000rpm.
Further, in step (3), centrifugal rotational speed 5000rpm.
Further, in step (3), the dosage of bis- (2- acetate) amine derivatives and bis- (pyridine ethyl) amine derivatives is
0.1-2 times of cellulose quality.
Further, in step (3), bis- (2- acetate) amine derivatives are bis- ((3- chlorine-2-hydroxyl) 2- acetates)
Propylamine.
Further, in step (3), bis- (pyridine ethyl) amine derivatives are bis- ((3- chlorine-2-hydroxyl) pyridine ethyls)
Propylamin hydrochloride.
The beneficial effects of the present invention are: the present invention provides a kind of " one kettle way " preparations to have the both sexes of " pincer " structure fine
The method for tieing up plain adsorbent, the amphoteric cellulose adsorbent material surface connection of the method for the present invention preparation be " pincer " structure from
Subtype group, this is more than the active group of single-stranded ionic group modified cellulose, and suction-operated is stronger, and side of the present invention
Method reaction step is few, and reaction condition is mild, easy to operate, is conducive to large-scale production.
Detailed description of the invention
Fig. 1 is the infared spectrum of amphoteric cellulose adsorbent made from embodiment 1.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A kind of preparation method of amphoteric cellulose adsorbent, includes the following steps:
(1) it weighs 20.0g NaOH and 10g urea and is added in 170g deionized water and dissolve, obtain sodium hydroxide-urea
5g microcrystalline cellulose is added in sodium hydroxide-aqueous solution of urea by aqueous solution, and 2000rpm stirs 10min, obtains cellulose
Suspension；
(2) it will thaw again, then stirred at 1000rpm mixed after -20 DEG C of cellulose suspension freezings for 24 hours of step (1)
It closes uniformly, obtains cellulose solution；
(3) cellulose solution of step (2) is centrifuged 30min under conditions of 5000rpm, takes supernatant, into supernatant according to
Secondary aqueous solution, bis- ((3- chlorine-2-hydroxyl) pyridine ethyls) containing 5g that bis- ((3- chlorine-2-hydroxyl) 2- acetate) propylamine Han 5g are added dropwise
The aqueous solution of propylamin hydrochloride, 100 DEG C at a temperature of be stirred to react 12h after, obtain reaction product, reaction product successively used
200mL deionized water, acetone, ether washing, then filter, are dried in vacuo 48h at room temperature, obtained product is amphoteric fibers
Plain adsorbent.
Structural characterization is carried out using amphoteric cellulose adsorbent of the infrared spectrum to embodiment 1, as a result as shown in Figure 1.Figure
In, 3428cm-1Neighbouring width and strong absorption peak are the stretching vibration peaks of-OH；2920cm-1The peak of left and right is-CH2Asymmetry
Stretching vibration peak；1632cm-1Neighbouring peak may be C=C stretching vibration peak or the flexural vibrations peak for adsorbing water；1031cm-1Place
Peak be to be generated by the asymmetric stretching vibration of C-O-C；1589cm-1And 1412cm-1Belong to carboxylic acid sodium (- COO-) asymmetry
Stretching vibration peak and symmetrical stretching vibration peak.1562cm-1And 1360cm-1Belong to the stretching vibration peak of C=N and C-N.
Embodiment 2
A kind of preparation method of amphoteric cellulose adsorbent, includes the following steps:
(1) it weighs 20.0g NaOH and 10g urea and is added in 170g deionized water and dissolve, obtain sodium hydroxide-urea
3g gossypin is added in sodium hydroxide-aqueous solution of urea by aqueous solution, and 2000rpm stirs 10min, and it is outstanding to obtain cellulose
Supernatant liquid；
(2) it will thaw again, then stirred at 1000rpm mixed after -20 DEG C of cellulose suspension freezings for 24 hours of step (1)
It closes uniformly, obtains cellulose solution；
(3) cellulose solution of step (2) is centrifuged 15min under conditions of 5000rpm, takes supernatant, into supernatant according to
The secondary aqueous solution that bis- ((3- chlorine-2-hydroxyl) 2- acetate) propylamine Han 1g are added dropwise, bis- ((3- chlorine-2-hydroxyl) pyridine second containing 0.8g
Base) propylamin hydrochloride aqueous solution, 80 DEG C at a temperature of be stirred to react 9h after, obtain reaction product, successively by reaction product
It is washed with 200mL deionized water, acetone, ether, then filters, is dried in vacuo 48h at room temperature, obtained product is both sexes fibre
Tie up plain adsorbent.
Comparative example 1
A kind of amphoteric cellulose, the preparation method comprises the following steps: by the sodium hydrate aqueous solution of cotton fiber immersion 17.5%, stirring
1h, static soak for 24 hours, are washed with water to neutrality after taking-up, filter, 45 DEG C of baking 6h, and alkali fiber is made.Weigh above-mentioned alkali fiber 5g
It is put into conical flask, 75mL ethyl alcohol is added, stir 5min, 20% sodium hydrate aqueous solution 50mL is added, is placed in 45 DEG C of water
It bathes in constant temperature oscillator, rises to 45 DEG C to mixed solution temperature in conical flask, the chloroethene aqueous acid 25mL of 5mol/L is added dropwise,
Cyclotron oscillation frequency is 100 times/min, reacts 45min, takes out solid content, is used again after being washed with 95% ethyl alcohol of 300mL point 3 times
Distillation washing 3 times filters, carboxymethyl cellulose (CMC) is made in 45 DEG C of baking 6h.It weighs CMC 1.6g to be put into conical flask, be added
60mL isopropanol stirs 5min, the 4% chloro- 2- Hydroxyproyl Trimethyl chlorination of sodium hydrate aqueous solution 12mL and 50%3- is added dropwise
Aqueous ammonium 6.0mL reacts 4h at 45 DEG C, and product is washed with water 2 times, then uses again after being washed with 95% ethyl alcohol of 300mL point 3 times
Distillation washing 3 times filters, amphoteric cellulose is made in 45 DEG C of baking 6h.
Comparative example 2
A kind of cation-modified cellulose, preparation method: PAN precursor is fixed on sample frame, hot in 250 DEG C of baking ovens
30min is handled, is made PAN pre-oxidized fibers (PANS fiber).PANS fiber uses dense sulfuric acid treatment 2h at room temperature, then spend from
Sub- water impregnates, until solution is neutrality, takes out and dries at 105 DEG C, obtains modified PAN fiber (SA-PANS fiber).
Comparative example 3
A kind of anion-modified cellulose, preparation method:
0.5g cellulose fibre is placed in 42mL and contains 0.69mol/L nitric acid, 4.34 × 10-2The water of mol/L ammonium ceric nitrate
Stirring, makes it be uniformly dispersed after in solution.System is led into N23mL Dimethylaminoethyl Methacrylate is added in 0.5h
(DMAEMA), continue logical N210min, closed system are transferred in 50 DEG C of water-baths and react 3h.After reaction terminates, wash repeatedly
Reaction product, vacuum drying, obtains the cellulose base adsorbent material for arsenic removal in water.
Performance test:
Embodiment 1 and 2 amphoteric cellulose adsorbent of embodiment are used to simulate the suction of heavy metal ion Pb (II) and As (V)
It is attached, while being compared with the cellulose adsorbent in comparative example 1-3, it the results are shown in Table 1.
Specific experiment method:
Take 200mg L-1Pb (II) solution 20mL, be added in the triangular flask of 50mL, adjust pH to 5.0, be then added
0.5–3g L-1Adsorbent, at room temperature adsorb 12 hours, after filtering measure solution in residue Pb (II) content, calculate suction
Attached amount.
Take 20mg L-1As (V) solution 20mL, be added in the triangular flask of 50mL, adjust pH to 1.0 ± 0.1, then plus
Enter 0.5-3g L-1Adsorbent, adsorb 12h at room temperature, after filtering measure solution in residue As (V) content, calculate adsorb
Amount and.
The different adsorbents of table 1 compare the maximal absorptive capacity qmax of Pb (II) and As (V)
From result above as it can be seen that compared with microcrystalline cellulose and modified cellulose reported in the literature, two prepared by the present invention
Property cellulose adsorbent ion pair Pb (II) and As (V) show stronger adsorption capacity, illustrate that the present invention is prepared into suction
Attached dose can be used as a kind of adsorbent material of good performance to handle the heavy metal cation and anion in waste water.
Claims (10)
1. a kind of preparation method of amphoteric cellulose adsorbent, which comprises the steps of:
(1) cellulose is added in sodium hydroxide-aqueous solution of urea, obtains cellulose suspension after mixing evenly；
(2) it thaws again after freezing the cellulose suspension of step (1), is then uniformly mixed, obtains cellulose solution；
(3) cellulose solution of step (2) is centrifuged, takes supernatant, bis- (2- acetate) amine derivatives are successively added dropwise into supernatant
Aqueous solution, bis- (pyridine ethyl) amine derivative aqueous solutions after being stirred to react 2-12h at a temperature of 50-100 DEG C, obtain reaction and produce
Object successively washs reaction product with deionized water, acetone, ether, then filters, is dry, and obtained product is both sexes fibre
Tie up plain adsorbent；
In step (1), the cellulose is microcrystalline cellulose or gossypin.
2. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (1), the hydrogen-oxygen
Change sodium-aqueous solution of urea in, sodium hydroxide, urea, deionized water weight ratio be 20:10:170.
3. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (1), speed of agitator
For 2000rpm, time 10min.
4. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (2), cryogenic temperature
It is -20 DEG C, the time is for 24 hours.
5. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (2), speed of agitator
For 1000rpm.
6. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (3), centrifugal rotational speed
For 5000rpm.
7. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that in step (3), bis- (2- second
Acidic group) dosages of amine derivative and bis- (pyridine ethyl) amine derivatives is 0.1-2 times of cellulose quality.
8. the preparation method of amphoteric cellulose adsorbent as described in claim 1, which is characterized in that described double in step (3)
(2- acetate) amine derivative is bis- ((3- chlorine-2-hydroxyl) 2- acetate) propylamine.
9. the preparation method of amphoteric cellulose adsorbent as described in any one of claim 1 to 8, which is characterized in that step (3)
In, in step (3), bis- (pyridine ethyl) amine derivatives are bis- ((3- chlorine-2-hydroxyl) pyridine ethyl) propylamin hydrochlorides.
10. application of the amphoteric cellulose adsorbent as water body purification adsorbent material made from claim 1-9 the method.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111214391A (en) * | 2019-11-25 | 2020-06-02 | 重庆东寰科技开发有限公司 | Amphoteric hydroxyethyl cellulose ether and preparation method thereof |
| CN113842894A (en) * | 2021-10-04 | 2021-12-28 | 桂林理工大学 | Preparation method and application of microcrystalline cellulose betaine ester adsorbent |
| CN114835826A (en) * | 2022-04-22 | 2022-08-02 | 深圳华源再生医学有限公司 | Zwitterionic cellulose and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626608A (en) * | 2012-04-16 | 2012-08-08 | 南京大学 | Straw modified into amphiprotic adsorbent and preparation method thereof |
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2018
- 2018-10-22 CN CN201811231679.XA patent/CN109400720A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102626608A (en) * | 2012-04-16 | 2012-08-08 | 南京大学 | Straw modified into amphiprotic adsorbent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 马芳: ""小麦秸秆及其纤维素的改性与吸附水体中Pb(II)和As(V)的机理研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111214391A (en) * | 2019-11-25 | 2020-06-02 | 重庆东寰科技开发有限公司 | Amphoteric hydroxyethyl cellulose ether and preparation method thereof |
| CN111214391B (en) * | 2019-11-25 | 2023-04-14 | 重庆东寰科技开发有限公司 | Amphoteric hydroxyethyl cellulose ether and preparation method thereof |
| CN113842894A (en) * | 2021-10-04 | 2021-12-28 | 桂林理工大学 | Preparation method and application of microcrystalline cellulose betaine ester adsorbent |
| CN114835826A (en) * | 2022-04-22 | 2022-08-02 | 深圳华源再生医学有限公司 | Zwitterionic cellulose and preparation method and application thereof |
| CN114835826B (en) * | 2022-04-22 | 2023-08-22 | 深圳华源再生医学有限公司 | Zwitterionic cellulose and preparation method and application thereof |
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Application publication date: 20190301 |