CN104587971B - A kind of preparation method of blotting chitosan adsorbent - Google Patents

A kind of preparation method of blotting chitosan adsorbent Download PDF

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Publication number
CN104587971B
CN104587971B CN201410800627.5A CN201410800627A CN104587971B CN 104587971 B CN104587971 B CN 104587971B CN 201410800627 A CN201410800627 A CN 201410800627A CN 104587971 B CN104587971 B CN 104587971B
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chitosan
temperature
adsorbent
reaction
solution
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CN104587971A (en
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党明岩
李壮志
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Shenyang Ligong University
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Shenyang Ligong University
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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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J2220/44—Materials comprising a mixture of organic materials
    • 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
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Cosmetics (AREA)

Abstract

The present invention discloses the preparation method of novel blotting chitosan adsorbent.React initially with Schiff base, protect a large amount of amino, so that it plays a role in adsorption process.Use diethylenetriamine to be grafted, considerably increase the active group of adsorbent.Carry out quaternary ammoniated, further enhancing the absorbability of adsorbent.After obtaining a large amount of adsorption group, carry out trace, it is thus achieved that more imprinted structures.Then using and self cross-link with the L cystine of adsorption group, the imprinted structures making formation is more stable, can form constitutionally stable memory hole after pickling.Adsorbent is to Cu2+, Ag+, Au3+Ion has the strongest adsorptive selectivity, and has the highest adsorption capacity, respectively up to 3.76mmol/g, 4.08mmol/g, 4.11mmol/g, acid and alkali-resistance at a temperature of 298K, does not runs off, and recycles more than 10 times, and absorption property is not decreased obviously.

Description

A kind of preparation method of blotting chitosan adsorbent
Technical field
The invention belongs to absorber material technical field, particularly relate to the preparation method of a kind of blotting chitosan adsorbent.
Background technology
Chitosan is the deacetylation product of chitin, and its molecule has active amino and hydroxyl, it is possible to the metal ion of chelating certain radius, so can use as metal ion adsorbent.Have a wide range of applications at aspects such as waste water process, medicine food, weaving, papermaking and Water warfare at present, be Novel environment-friendlymaterial material.
Including a lot to the method for modifying of chitosan, such as acylation modification, Shiff alkali reaction, cross-linking modified, alkylation modification, esterification modification, trace is modified, graft modification etc..For current progress, a kind of method of employing is concentrated mainly on for the modification of chitosan chitosan is carried out chemical modification, it is impossible to concentrate the advantage of multiple method of modifying, to obtain performance more preferably chitosan derivatives.This makes chitosan derivative physical performance after being chemically modified the most single.
Blotting obtains in recent years to be studied widely and applies.But, first increase adsorption group by the method for grafting, form more imprinted structures, then the research carrying out cross-linking rarely has report.Liu Ping Jie etc. utilize dithiocar-bamate that chitosan is carried out graft modification, then use Pb2+For trace ion, synthesize a kind of novel trace adsorbent, to Pb2+There is preferable adsorption effect.But the adsorption group or fewer that dithiocar-bamate is introduced.The method also cross-links simultaneously, makes the memory hole structural instability of formation, is also easily caused chitosan molecule and runs off in acid condition.
Summary of the invention
The defect that the present invention exists to overcome prior art, it is an object of the invention to provide a kind of adsorbent imprinted structures more, the preparation method of the novel blotting chitosan adsorbent that adsorbance is bigger.
The adopted technical solution is that the preparation method of a kind of blotting chitosan adsorbent, its method step is as follows:
Step 1: formaldehyde is added in chitosan solution and reacts；
Step 2: solution and the mixing of 2 ~ 15ml epoxychloropropane that step 1 prepares add microwave reactor and carry out microwave heating, reaction 10 ~ 60min is stirred under the conditions of 40 ~ 80 DEG C, it is subsequently added 2 ~ 10ml diethylenetriamine at a temperature of 40 ~ 80 DEG C, stirs reaction 10 ~ 60min, it is eventually adding 5 ~ 30ml triethylamine and carries out graft reaction, at a temperature of 40 ~ 80 DEG C, stir reaction 10 ~ 60min；The sintetics distilled water obtained, ethanol, acetone cleans sucking filtration repeatedly, gets rid of the Organic substance of attachment；
Step 3: the sulfuric acid solution of 0.1 ~ 0.5mol/L is added the chitosan derivatives obtained through step 2, at a temperature of 40 ~ 80 DEG C, constant temperature oscillation 5 ~ 10h, then with distilled water cyclic washing to neutral；
Step 4: will obtain the metal ion solution that chitosan derivatives adds 0.5 ~ 2mol/L from step 3, and in microwave reactor, temperature 40 ~ 60 DEG C will be set, stirs reaction 30 ~ 60min；
Step 5: CYSTINE is added ultrasonic dissolution 30 ~ 90min in the hydrochloric acid solution that mass fraction is 2%, adds the chitosan derivatives that step 4 obtains afterwards, in microwave reactor, temperature 40 ~ 80 DEG C is set, stirs reaction 30 ~ 90min；
Step 6: step 5 obtained in the sulfuric acid solution that chitosan derivatives adds 0.1 ~ 1mol/L, reacts 8 ~ 24h under 40 ~ 80 DEG C of constant temperature oscillations；Then the chitosan derivatives after eluting metal ion is the most neutral with distilled water cyclic washing, to dry in 50 DEG C of vacuum desiccators, the product after drying is put in exsiccator after grinding and is stored for future use；
Chitosan is dissolved in the acetic acid solution that mass fraction is 0.2 ~ 2% by described step 1, is the chitosan solution that 50% formaldehyde adds acetic acid by 3 ~ 30ml concentration, under the conditions of 40 ~ 80 DEG C, stir reaction 20 ~ 60 min.The concentration of formaldehyde is mass fraction concentration.
The metal ion of the metal ion solution in step 4 is Cu2+Or Ag+Or Au3+Solution.
Compared with prior art, the present invention is had the beneficial effect that to react initially with Schiff base, protects a large amount of amino, so that it plays a role in adsorption process.Use diethylenetriamine to be grafted, considerably increase the active group of adsorbent.Carry out quaternary ammoniated, further enhancing the absorbability of adsorbent.After obtaining a large amount of adsorption group, carry out trace, it is thus achieved that more imprinted structures.Then using and self cross-link with the CYSTINE of adsorption group, the imprinted structures making formation is more stable, can form constitutionally stable memory hole after pickling.Adsorbent is to Cu2+, Ag+, Au3+Ion has the strongest adsorptive selectivity, and has the highest adsorption capacity, respectively up to 3.76mmol/g, 4.08mmol/g, 4.11mmol/g, acid and alkali-resistance at a temperature of 298K, does not runs off, and recycles more than 10 times, and absorption property is not decreased obviously.
Detailed description of the invention
Embodiment 1:
A kind of preparation method of blotting chitosan adsorbent, its method step is as follows:
Step 1: take 5g and dissolved in the acetic acid solution that mass fraction is 1% by chitosan, is the chitosan solution that 50% formaldehyde adds acetic acid by 20ml concentration, stirring reaction 50 min under the conditions of 80 DEG C.There is Schiff base reaction.
Step 2: the chitosan solution of generation Schiff base reaction step 1 prepared mixes microwave heating in addition three neck round bottom flask with 10ml epoxychloropropane, stirring reaction 30min under the conditions of 60 DEG C, it is subsequently added 9ml diethylenetriamine at a temperature of 60 DEG C, stirs reaction 30min, it is eventually adding 15ml triethylamine and carries out graft reaction, stirring reaction 30min at a temperature of 60 DEG C；The sintetics distilled water obtained, ethanol, acetone cleans sucking filtration repeatedly, gets rid of the Organic substance of attachment；
Step 3: the sulfuric acid solution 40ml of 0.2mol/L is added the chitosan derivatives obtained through step 2, at a temperature of 70 DEG C, constant temperature oscillation 8h, then with distilled water cyclic washing to neutral；
Step 4: will obtain, from step 3, the Cu that chitosan derivatives adds 1mol/L2+In solion, in microwave reactor, temperature 50 C, stirring reaction 40min are set；
Step 5: 2g CYSTINE adds ultrasonic dissolution 50min in the hydrochloric acid solution that 30ml mass fraction is 2%, adds the chitosan derivatives through above-mentioned printing process that step 4 obtains afterwards, in microwave reactor, arranges temperature 50 C, stirring reaction 600min；Crosslink reaction.
Step 6: step 5 obtained in the sulfuric acid solution that chitosan derivatives adds 0.5mol/L, reacts 12h under 60 DEG C of constant temperature oscillations；Then the chitosan derivatives after eluting metal ion is the most neutral with distilled water cyclic washing, to dry in 50 DEG C of vacuum desiccators, the product after drying is put in exsiccator after grinding and is stored for future use；
Weigh 2g novel blotting chitosan adsorbent, add the Cu of 1mol/L2+In solion 25ml, adsorption capacity is 3.76mmol/g.
Embodiment 2:
A kind of preparation method of blotting chitosan adsorbent, its method step is as follows:
Step 1: dissolved in the acetic acid solution that mass fraction is 0.2% by chitosan, is the chitosan solution that 50% formaldehyde adds acetic acid by 3ml concentration, stirring reaction 20 min under the conditions of 40 DEG C.There is Schiff base reaction.
Step 2: solution and the mixing of 2 ~ 15ml epoxychloropropane that step 1 prepares add microwave reactor and carry out microwave heating, stirring reaction 10min under the conditions of 40 DEG C, it is subsequently added 2ml diethylenetriamine at a temperature of 40 DEG C, stirs reaction 10min, it is eventually adding 5ml triethylamine and carries out graft reaction, stirring reaction 10min at a temperature of 40 DEG C；The sintetics distilled water obtained, ethanol, acetone cleans sucking filtration repeatedly, gets rid of the Organic substance of attachment；
Step 3: the sulfuric acid solution of 0.15mol/L is added the chitosan derivatives obtained through step 2, at a temperature of 40 DEG C, constant temperature oscillation 5h, then with distilled water cyclic washing to neutral；
Step 4: will obtain, from step 3, the Ag that chitosan derivatives adds 1mol/L+In solion, in microwave reactor, temperature 40 DEG C, stirring reaction 30min are set；
Step 5: 2g CYSTINE adds ultrasonic dissolution 30min in the hydrochloric acid solution that 30ml mass fraction is 2%, adds the chitosan derivatives through above-mentioned printing process that step 4 obtains afterwards, in microwave reactor, arranges temperature 40 DEG C, stirring reaction 30min；Crosslink reaction.
Step 6: step 5 obtained in the sulfuric acid solution that chitosan derivatives adds 0.1mol/L, reacts 8h under 40 DEG C of constant temperature oscillations；Then the chitosan derivatives after eluting metal ion is the most neutral with distilled water cyclic washing, to dry in 50 DEG C of vacuum desiccators, the product after drying is put in exsiccator after grinding and is stored for future use；
Weigh 2g novel blotting chitosan adsorbent, add the Ag of 1mol/L+In solion 25ml, adsorption capacity is 4.08mmol/g.
Embodiment 3:
A kind of preparation method of blotting chitosan adsorbent, its method step is as follows:
Step 1: dissolved in the acetic acid solution that mass fraction is 2% by chitosan, is the chitosan solution that 50% formaldehyde adds acetic acid by 30ml concentration, stirring reaction 60 min under the conditions of 80 DEG C.There is Schiff base reaction.
Step 2: the solution that step 1 prepares mixes addition microwave reactor and carries out microwave heating with 15ml epoxychloropropane, stirring reaction 60min under the conditions of 80 DEG C, it is subsequently added 10ml diethylenetriamine at a temperature of 80 DEG C, stirs reaction 60min, it is eventually adding 30ml triethylamine and carries out graft reaction, stirring reaction 60min at a temperature of 80 DEG C；The sintetics distilled water obtained, ethanol, acetone cleans sucking filtration repeatedly, gets rid of the Organic substance of attachment；
Step 3: the sulfuric acid solution of 0.5mol/L is added the chitosan derivatives obtained through step 2, at a temperature of 80 DEG C, constant temperature oscillation 10h, then with distilled water cyclic washing to neutral；
Step 4: will obtain, from step 3, the Au that chitosan derivatives adds 2mol/L3+Solion, in microwave reactor, arranges temperature 60 C, stirring reaction 60min；
Step 5: 2g CYSTINE adds ultrasonic dissolution 90min in the hydrochloric acid solution that 30ml mass fraction is 2%, adds the chitosan derivatives through above-mentioned printing process that step 4 obtains afterwards, in microwave reactor, arranges temperature 80 DEG C, stirring reaction 90min；Crosslink reaction.
Step 6: step 5 obtained in the sulfuric acid solution that chitosan derivatives adds 1mol/L, reacts 24h under 80 DEG C of constant temperature oscillations；Then the chitosan derivatives after eluting metal ion is the most neutral with distilled water cyclic washing, to dry in 50 DEG C of vacuum desiccators, the product after drying is put in exsiccator after grinding and is stored for future use；
Weigh 2g novel blotting chitosan adsorbent, add the Au of 1mol/L3+In solion 25ml, adsorption capacity is 4.11mmol/g.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements both fall within scope of the claimed invention.Claimed scope is defined by appending claims and equivalent thereof.

Claims (2)

1. the preparation method of a blotting chitosan adsorbent, it is characterised in that: its method step is as follows:
Step 1: formaldehyde is added in chitosan solution and reacts；
Step 2: solution and the mixing of 2 ~ 15ml epoxychloropropane that step 1 prepares add microwave reactor and carry out microwave heating, reaction 10 ~ 60min is stirred under the conditions of 40 ~ 80 DEG C, it is subsequently added 2 ~ 10ml diethylenetriamine at a temperature of 40 ~ 80 DEG C, stirs reaction 10 ~ 60min, it is eventually adding 5 ~ 30ml triethylamine and carries out graft reaction, at a temperature of 40 ~ 80 DEG C, stir reaction 10 ~ 60min；The sintetics distilled water obtained, ethanol, acetone cleans sucking filtration repeatedly, gets rid of the Organic substance of attachment；
Step 3: the sulfuric acid solution of 0.1 ~ 0.5mol/L is added the chitosan derivatives obtained through step 2, at a temperature of 40 ~ 80 DEG C, constant temperature oscillation 5 ~ 10h, then with distilled water cyclic washing to neutral；
Step 4: will obtain the metal ion solution that chitosan derivatives adds 0.5 ~ 2mol/L from step 3, and in microwave reactor, temperature 40 ~ 60 DEG C will be set, stirs reaction 30 ~ 60min；
Step 5: CYSTINE is added ultrasonic dissolution 30 ~ 90min in the hydrochloric acid solution that mass fraction is 2%, adds the chitosan derivatives that step 4 obtains afterwards, in microwave reactor, temperature 40 ~ 80 DEG C is set, stirs reaction 30 ~ 90min；
Step 6: step 5 obtained in the sulfuric acid solution that chitosan derivatives adds 0.1 ~ 1mol/L, reacts 8 ~ 24h under 40 ~ 80 DEG C of constant temperature oscillations；Then the chitosan derivatives after eluting metal ion is the most neutral with distilled water cyclic washing, to dry in 50 DEG C of vacuum desiccators, the product after drying is put in exsiccator after grinding and is stored for future use.
The preparation method of blotting chitosan adsorbent the most according to claim 1, it is characterized in that: chitosan is dissolved in the acetic acid solution that mass fraction is 0.2 ~ 2% by described step 1, it is the chitosan solution that 50% formaldehyde adds acetic acid by 3 ~ 30ml concentration, under the conditions of 40 ~ 80 DEG C, stirs reaction 20 ~ 60 min.
CN201410800627.5A 2014-12-22 2014-12-22 A kind of preparation method of blotting chitosan adsorbent Expired - Fee Related CN104587971B (en)

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