CN105396561A - Preparation method for holocellulose/chitosan microsphere adsorbent - Google Patents

Abstract

The invention relates to a preparation method for a holocellulose/chitosan microsphere adsorbent, belonging to the field of preparation of an adsorption material. The method is directed at the problems of poor adsorption capability and need for chemical modification and crosslinking of a conventional cellulose adsorbent and comprises the following steps: subjecting soybean straw to degreasing and decoloring and then to hydrolysis so as to prepare a chitosan microsphere particle; then compounding the chitosan microsphere particle with holocellulose; extracting a mixture obtained in the previous step with ethyl acetate in a Soxhlet extraction apparatus; and carrying out drying so as to prepare the holocellulose/chitosan microsphere adsorbent. Accordin gto the invention, the holocellulose/chitosan microsphere adsorbent prepared from the soybean straw has heavy metal ion adsorption capacity of more than 90%; and preparation of the adsorbent from the soybean straw reduces cost and is green, environment-friendly and pollution-free.

Description

The preparation method of a kind of holocellulose/chitosan microball adsorbent

Technical field

The present invention relates to the preparation method of a kind of holocellulose/chitosan microball adsorbent, belong to sorbing material preparation field.

Background technology

Cellulose is eco-friendly macromolecular material, take cellulose as matrix, replace synthesis macromolecule matrix expensive at present, carry out the research of cellulose base functional nanocomposite, significantly can reduce the preparation cost of composite, what promote this type of material applies that poor, the easy decomposition of organic antibacterial agent heat endurance, persistence are poor, toxicity is comparatively large and use harmful for a long time usually, and in order to overcome the shortcoming of organic antibacterial agent, research direction is turned to inorganic antiseptic by people gradually.

Modified natural fibers element ABSORBENTS ABSORPTION metal biosorption has lot of advantages, therefore, in recent years, resource scarcity modified cellulose is used widely in environmental improvement heavy metal process row, and the preparation synthesis adsorbent of high adsorption and the regenerative agent of high reproducibility become current particularly important research point.

Summary of the invention

Technical problem to be solved by this invention: for adopting cellulose as adsorbent at present, adsorption capacity is poor and need to its chemical modification and crosslinked problem, provide one and carry out degreasing and decolouring by soybean stalk, it is hydrolyzed and prepares chitosan microball particle, subsequently by chitosan microball particle and brown cellulose compound, in soxhlet type apparatus, extracting is carried out by ethyl acetate, to its dry preparation a kind of holocellulose/chitosan microball adsorbent, this adsorbent Be very effective and easy to make.

For solving the problems of the technologies described above, the present invention adopts technical scheme as described below to be:

(1) soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 3 ~ 5 days, be placed in high speed grinding mill and carry out pulverizing and sieving to it, collect 80 ~ 100 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 20 ~ 30 DEG C, be prepared into extract;

(2) be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 5 ~ 6h, decolouring paraffin removal is carried out 1 ~ 2 time repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 1 ~ 2 time more subsequently, remove stalk particle pigment and wax;

(3) after Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 70 ~ 75 DEG C of insulated and stirred reaction 1 ~ 2h are warming up to it, subsequently acetic acid solution adjustment pH to 4.2 ~ 4.5 that mass fraction is 5% are added to it, and to its pressure filtration, collect filter cake and be placed on dry 6 ~ 8h in the baking oven of 60 ~ 70 DEG C, obtaining holocellulose for subsequent use;

(4) ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 2.5 ~ 3.0, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 45 ~ 65 parts, 20 ~ 30 parts of mass concentrations are the sodium tripolyphosphate solution of the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the 2g/L of 15 ~ 25 parts, are uniformly mixed formation crosslinker solution at 20 ~ 30 DEG C;

(5) after end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 20 ~ 24h in Soxhlet extraction device respectively, take out filter cake dry 20 ~ 30min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier;

(6) count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 20 ~ 45 parts, the deionized water of 35 ~ 50 parts and 20 ~ 25 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 80 ~ 90 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 55 ~ 60 DEG C of baking ovens, dry 6 ~ 10h can be prepared into a kind of holocellulose/chitosan microball adsorbent.

Application process of the present invention is: getting holocellulose/chitosan microball sorbent-loaded that 20 ~ 40g obtains is on the screen cloth of 20 μm in aperture, being holded up by screen cloth is placed in wastewater disposal basin, one is laid every 50 ~ 60cm, pass into the mercury-containing waste water that mass concentration is 20 ~ 200mg/L, stop 6 ~ 8h, recording mercury ion adsorption capacity is 18 ~ 190mg/g, and adsorption rate reaches more than 90%.

The present invention is compared with additive method, and Advantageous Effects is:

(1) the present invention prepares holocellulose/chitosan microball adsorbent by soybean stalk, and heavy metal ionic adsorption effect reaches more than 90%;

(2) prepare adsorbent by soybean stalk, reduce costs, environmental protection is pollution-free.

Detailed description of the invention

First soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 3 ~ 5 days, be placed in high speed grinding mill and carry out pulverizing and sieving to it, collect 80 ~ 100 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 20 ~ 30 DEG C, be prepared into extract; Be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 5 ~ 6h, decolouring paraffin removal is carried out 1 ~ 2 time repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 1 ~ 2 time more subsequently, remove stalk particle pigment and wax; After Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 70 ~ 75 DEG C of insulated and stirred reaction 1 ~ 2h are warming up to it, subsequently acetic acid solution adjustment pH to 4.2 ~ 4.5 that mass fraction is 5% are added to it, and to its pressure filtration, collect filter cake and be placed on dry 6 ~ 8h in the baking oven of 60 ~ 70 DEG C, obtaining holocellulose for subsequent use; The ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 2.5 ~ 3.0, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 45 ~ 65 parts, mass concentration is the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the sodium tripolyphosphate solution of 2g/L, is uniformly mixed formation crosslinker solution at 20 ~ 30 DEG C; After end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 20 ~ 24h in Soxhlet extraction device respectively, take out filter cake dry 20 ~ 30min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier; Count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 20 ~ 45 parts, the deionized water of 35 ~ 50 parts and 20 ~ 25 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 80 ~ 90 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 55 ~ 60 DEG C of baking ovens, dry 6 ~ 10h can be prepared into a kind of holocellulose/chitosan microball adsorbent.

Example 1

First soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 3 days, being placed in high speed grinding mill and carrying out pulverizing and sieving to it, collect 80 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 20 DEG C, be prepared into extract; Be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 5h, decolouring paraffin removal is carried out 1 time repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 1 time more subsequently, remove stalk particle pigment and wax; After Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 70 DEG C of insulated and stirred reaction 1h are warming up to it, subsequently the acetic acid solution adjustment pH to 4.2 that mass fraction is 5% is added to it, and to its pressure filtration, collect filter cake and be placed on dry 6h in the baking oven of 60 DEG C, obtaining holocellulose for subsequent use; The ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 2.5 ~ 3.0, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 45 parts, 30 parts of mass concentrations are the sodium tripolyphosphate solution of the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the 2g/L of 25 parts, are uniformly mixed formation crosslinker solution at 20 DEG C; After end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 20h in Soxhlet extraction device respectively, take out filter cake dry 20min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier; Count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 20 parts, the deionized water of 50 parts and 25 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 80 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 55 DEG C of baking ovens, dry 6h can be prepared into a kind of holocellulose/chitosan microball adsorbent.

Getting holocellulose/chitosan microball sorbent-loaded that 20g obtains is on the screen cloth of 20 μm in aperture, being holded up by screen cloth is placed in wastewater disposal basin, one is laid every 50cm, pass into the mercury-containing waste water that mass concentration is 20mg/L, stop 6h, recording mercury ion adsorption capacity is 18mg/g, and adsorption rate reaches 90%.

Example 2

First soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 4 days, being placed in high speed grinding mill and carrying out pulverizing and sieving to it, collect 90 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 25 DEG C, be prepared into extract; Be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 5.5h, decolouring paraffin removal is carried out 1 time repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 1 time more subsequently, remove stalk particle pigment and wax; After Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 72 DEG C of insulated and stirred reaction 1.5h are warming up to it, subsequently the acetic acid solution adjustment pH to 4.3 that mass fraction is 5% is added to it, and to its pressure filtration, collect filter cake and be placed on dry 7h in the baking oven of 65 DEG C, obtaining holocellulose for subsequent use; The ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 2.7, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 50 parts, 25 parts of mass concentrations are the sodium tripolyphosphate solution of the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the 2g/L of 25 parts, are uniformly mixed formation crosslinker solution at 25 DEG C; After end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 22h in Soxhlet extraction device respectively, take out filter cake dry 25min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier; Count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 30 parts, the deionized water of 45 parts and 25 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 85 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 58 DEG C of baking ovens, dry 8h can be prepared into a kind of holocellulose/chitosan microball adsorbent.

Getting holocellulose/chitosan microball sorbent-loaded that 30g obtains is on the screen cloth of 20 μm in aperture, being holded up by screen cloth is placed in wastewater disposal basin, one is laid every 55cm, pass into the mercury-containing waste water that mass concentration is 100mg/L, stop 7h, recording mercury ion adsorption capacity is 100mg/g, and adsorption rate reaches 92%.

Example 3

First soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 5 days, being placed in high speed grinding mill and carrying out pulverizing and sieving to it, collect 100 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 30 DEG C, be prepared into extract; Be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 6h, decolouring paraffin removal is carried out 2 times repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 2 times more subsequently, remove stalk particle pigment and wax; After Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 75 DEG C of insulated and stirred reaction 2h are warming up to it, subsequently the acetic acid solution adjustment pH to 4.5 that mass fraction is 5% is added to it, and to its pressure filtration, collect filter cake and be placed on dry 8h in the baking oven of 70 DEG C, obtaining holocellulose for subsequent use; The ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 3.0, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 65 parts, the mass concentration of 20 parts is the sodium tripolyphosphate solution of the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the 2g/L of 15 parts, is uniformly mixed formation crosslinker solution at 30 DEG C; After end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 24h in Soxhlet extraction device respectively, take out filter cake dry 30min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier; Count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 45 parts, the deionized water of 35 parts and 20 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 90 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 60 DEG C of baking ovens, dry 10h can be prepared into a kind of holocellulose/chitosan microball adsorbent.

Getting holocellulose/chitosan microball sorbent-loaded that 40g obtains is on the screen cloth of 20 μm in aperture, being holded up by screen cloth is placed in wastewater disposal basin, one is laid every 60cm, pass into the mercury-containing waste water that mass concentration is 200mg/L, stop 8h, recording mercury ion adsorption capacity is 190mg/g, and adsorption rate reaches 95%.

Claims (1)

1. a preparation method for holocellulose/chitosan microball adsorbent, is characterized in that concrete preparation process is:

(1) soybean stalk is rinsed through clear water, after being exposed to the sun under sunlight 3 ~ 5 days, be placed in high speed grinding mill and carry out pulverizing and sieving to it, collect 80 ~ 100 object soybean stalk particles, subsequently by the ratio of methyl alcohol and toluene 5:1 by volume, be uniformly mixed at 20 ~ 30 DEG C, be prepared into extract;

(2) be the ratio of 1:3 in solid-to-liquid ratio, by the soybean stalk particle of above-mentioned preparation and extract, be placed in Soxhlet extraction device, after its Soxhlet extraction 5 ~ 6h, decolouring paraffin removal is carried out 1 ~ 2 time repeatedly again by macroporous resin column, in micropore gel column, carry out secondary decolourization paraffin removal 1 ~ 2 time more subsequently, remove stalk particle pigment and wax;

(3) after Soxhlet extraction completes, 1:5 in mass ratio, the sodium hydroxide solution of the soybean stalk particle after extracting and 0.85mol/L is uniformly mixed, and 70 ~ 75 DEG C of insulated and stirred reaction 1 ~ 2h are warming up to it, subsequently acetic acid solution adjustment pH to 4.2 ~ 4.5 that mass fraction is 5% are added to it, and to its pressure filtration, collect filter cake and be placed on dry 6 ~ 8h in the baking oven of 60 ~ 70 DEG C, obtaining holocellulose for subsequent use;

(4) ratio of 1:250 in mass ratio, Chitosan powder being dissolved to mass concentration is in the acetum of 2%, regulate pH to 2.5 ~ 3.0, be prepared into chitosan solution, count by weight subsequently, choose the chitosan solution of 45 ~ 65 parts, 20 ~ 30 parts of mass concentrations are the sodium tripolyphosphate solution of the different thiophene of the methyl mile beautiful jade ketone solution of 10% and the 2g/L of 15 ~ 25 parts, are uniformly mixed formation crosslinker solution at 20 ~ 30 DEG C;

(5) after end to be crosslinked, washing crosslinker solution to pH by deionized water is 7, subsequently to its suction filtration, collect filter cake, and use ethyl acetate and acetone extracting 20 ~ 24h in Soxhlet extraction device respectively, take out filter cake dry 20 ~ 30min in 50 DEG C of baking ovens subsequently, be prepared into chitosan microball carrier;

(6) count by weight, choose the holocellulose of above-mentioned preparation of the chitosan microball carrier of 20 ~ 45 parts, the deionized water of 35 ~ 50 parts and 20 ~ 25 parts, be prepared into shitosan mixed liquor, be placed on subsequently in there-necked flask, reflux 1h under 80 ~ 90 DEG C of waters bath with thermostatic control, after backflow completes, decompress filter is carried out to it, collect filter cake, and distilled water washing is 7.0 to pH, in 55 ~ 60 DEG C of baking ovens, dry 6 ~ 10h can be prepared into a kind of holocellulose/chitosan microball adsorbent.