CN104086785B - A kind of bamboo shoots leftover bits and pieces is carried out to method and the application thereof that composite aquogel is prepared in modification - Google Patents
A kind of bamboo shoots leftover bits and pieces is carried out to method and the application thereof that composite aquogel is prepared in modification Download PDFInfo
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Abstract
The invention provides and a kind of bamboo shoots leftover bits and pieces is carried out to method and the application thereof that composite aquogel is prepared in modification, described sorbing material is extracted after cellulose by bamboo shoots leftover bits and pieces that to carry out carrying out after modification epoxychloropropane with sodium chloroacetate crosslinked, inverse suspension polymerization afterwards, finally carries out freeze drying and forms. This invent and prepare hydrogel beads and set it as a kind of biological adsorption agent, taking methylene blue as dyestuff Model Molecule, study its adsorption effect to methylene blue, be absorption and the slowly-releasing based theoretical of this hydrogel. The present invention utilizes the discarded leftover bits and pieces of bamboo shoots processing to prepare composite aquogel, raw material sources are abundant, with low cost, can realize twice laid, promote recycling economy, prepared hydrogel can be applied to the absorption of waste water from dyestuff, and the absorption of model drug and slowly-releasing, reduce bamboo shoots leftover bits and pieces and arbitrarily abandon the pollution to environment, can in promotion ecological resources Green Development, play a role.
Description
Technical field
The present invention relates to method and the application thereof of composite aquogel, be specifically related to one bamboo shoots leftover bits and pieces carry out modification systemMethod and the application thereof of standby composite aquogel.
Background technology
Bamboo shoots (Bambooshoot) are a kind of aboundresources, the edible plants that output is higher. Bamboo shoots are that bamboo is becomingUnique bud stem that expands that the long initial stage has, its matter is tender delicious, contains abundant essential amino acid, mineral element, dimensionThe fibre compositions that raw element and being difficult to is digested by human body etc. are that one has the natural food materials of nutritive value. Due to woods in recent yearsGround bamboo shoots plantation is constantly applied, since 2010, and 5,000,000-6,000,000 tons, every annual output bamboo shoots, except 40% marketing fresh, all the otherAll for the processing of can bamboo shoot and dried bamboo shoots.
In bamboo shoots for make the bamboo shoot meat of the bamboo shoot product such as Bamboo shoots, dry bamboo shoot only account for whole bamboo shoot body compared with small part, with hairBamboo shoots are example, and its bamboo shoot meat accounts for 28%, and all the other are the leftover bits and pieces such as bamboo shoot head and bamboo shoot shell, and it is because rough wearing fiber composition is up to 72%,Therefore in process, be discarded, and in these leftover bits and pieces that not yet effectively utilize nutrition and health care composition is comparatively speakingAlso lower, be not processed to food. So, in the process of bamboo shoots processing, all can produce a large amount of processing wastes---Leftover bits and pieces, if these accessory substance processing is bad, will cause the wasting of resources and environmental pollution, will to people's production,Life and health have a negative impact, and cause the waste of biomass resource. So, to the recycling of processing wasteResearch just seem extremely important. Therefore, the application technology of research bamboo shoots processing waste just has possibility.
Along with the day by day worry of people to petroleum resources exhaustion, replace oil money by renewable natural agricultural-forestry biomassSource, synthesis of natural macromolecular material has obtained increasing concern. Processing of farm products discarded object is inexhaustible use on the earthInexhaustible renewable resource, these natural polymers have various structures and functional group, are easy to chemistry and physical modification, withTime there is the feature such as biological degradability and biological safety. Therefore, the asparagus leftover bits and pieces skin slag in processing of farm products is repaiiedDecorations modification, synthesis of natural macromolecule hydrogel material, for curbing environmental pollution, medicine control discharges, is to a certain extentThe processing processing of asparagus leftover bits and pieces has provided certain solution, significant.
The invention provides a kind of novel by the cellulose modified method of preparing composite aquogel of bamboo shoots, with discard bamboo shoots get a footholdMaterial slag is primary raw material, extracts bamboo shoots cellulose after the bleaching to bamboo shoots, basification, then to the bamboo shoots that extractCellulose carries out carboxymethyl-modification. Form water-setting colloid structure feature for independent carboxy methylation bamboo shoots cellulose not idealProblem, improve the texture characteristic of hydrogel by adding kappa-carrageenan. Finally, pass through to regulate by via Inverse-Phase Suspension PolymerizationRotor speed, rotor and reactor diameter ratio, atoleine volume is prepared hydrogel beads, sets it as one after freeze dryingBiological adsorption agent, because this hydrogel contains a large amount of negative electrical charge such as carboxymethyl and sulfinyl group groups, according to positive and negative charge phaseThe theory of absorption is studied its absorption property to model dye of positive ion methylene blue.
Summary of the invention
The present invention is devoted to by bamboo shoots leftover bits and pieces is carried out to modification, provides a kind of bamboo shoots leftover bits and pieces is carried out to modification preparationThe method of composite aquogel and application thereof, this adsorbent, taking bamboo shoots leftover bits and pieces as primary raw material, adds kappa-carrageenan and improves waterGel texture characteristic carries out modification by itself and sodium chloroacetate in isopropyl alcohol, and epoxychloropropane is cross-linked, finally by anti-Phase suspension polymerization and the hydrogel beads that makes.
Bamboo shoots are carried out to modification and prepare the method for hydrogel beads as biological adsorption agent, described composite aquogel is by bambooBamboo shoot leftover bits and pieces extracts after cellulose that to carry out carrying out after modification epoxychloropropane with sodium chloroacetate crosslinked, inverse suspension polymerization afterwards,Finally carry out freeze drying and form, concrete steps are:
(1) bamboo shoots leftover bits and pieces is through washing, oven drying 12-16h, and baking temperature is 70-80 DEG C or dries in the sun,The dry shape that is cut into small pieces afterwards, is convenient to pulverize, and pulverizes 80 mesh sieves afterwards through pulverizer, obtains bamboo shoots ground-slag end for subsequent use;
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to material water quality than the ratio of 1:20-1:25, at 65-80 DEG CUnder condition, complete and process 2h-2.5h passivation bamboo shoots active enzyme, regulate with the glacial acetic acid of mass fraction 10%-15% afterwardsPH value of solution, at 3.8-4.0, after adjusting, adds sodium chlorite to carry out bleaching, under 75-80 DEG C of condition, carry out bleaching placeReason, to remove the lignin in bamboo shoots leftover bits and pieces;
(3) after bleaching, insoluble flocculent substance in filtering solution, and wash with distilled water that it is colourless to filtrate,Rear service property (quality) mark 85%-95% ethanol carries out alcohol wash, is finally dried and processes 16-20h in 50-70 DEG C of baking oven, obtainsPretreatment bamboo shoots fiber; Be denoted as PBSC (PretreatmentBambooShootCellulose)
(4) dry pretreatment bamboo shoots fiber is later pulverized, crossed 80 mesh sieves, according to solid-liquid ratio 1:15-1:20 (g/Ml) join potassium hydroxide aqueous solution and stir alkalization 12h-20h, the object of basification is in order to remove half fiber in PBSCElement, reaction finishes the PBSC that rear taking-up was processed, and washing, puts into baking oven and process 16-20h at 50-70 DEG C, after being dried,To bamboo shoots cellulose after de-hemicellulose, be denoted as BSC (BambooSheetCellulose);
(5) bamboo shoots cellulose after the de-hemicellulose being dried after processing is pulverized, after pulverizing, crossed 80 mesh sieves;
(6) modified technique is as follows: after accurately weighing the de-hemicellulose of 10-12g, bamboo shoots cellulose adds in reactor, afterwardsAdd distilled water and isopropyl alcohol, then after adding the mass fraction of 80-100ul to be 30%-35% hydrogen peroxide, shake up, shake upAdding afterwards mass fraction is 40%-50%NaOH solution 16-20ml, carries out basification, and alkalization time is 2-3h, makes baseThe hydroxyl of 2,4,6 on this all fibres element molecule can activate, and alkalizes complete, and bamboo shoots cellulose obtains alkalizing;
(7) the modification stage adds sodium chloroacetate solution in reactor, starts gradient increased temperature etherificate, and reactant liquor is at magnetic forceUnder stirring condition, in room temperature treatment 30-50min, be transferred to afterwards shaking table and carry out 40-45 DEG C of shaking water bath 30-40min, Zhi HoujinRow 55-60 DEG C of shaking water bath 30-40min, then carry out 75-80 DEG C of high-temperature process 80-90min;
(8) recover after completion of the reaction room temperature, again adding 6ml mass fraction is that 50%NaOH solution carries out double alkalisation,Alkalization time is 30min, carries out secondary etherificate after alkalization, and etherificate concrete technology is with consistent in temperature parameter same (7);
(9), after treating etherificate, supernatant discarded after cool to room temperature is poured 300-into after the spherical dope of lower floor is coolingThe processing of 500ml methyl alcohol, shaking table room temperature concussion 30-40min, washes away unreacted component and other impurity wherein, stratificationAfter outwell upper strata alcohol liquid, again add after being adjusted to neutrality with glacial acetic acid after hold over night after concussion after 300-500ml methyl alcohol and stirMix rear leaving standstill and outwell upper strata alcohol liquid, carry out ethanol and wash, after cleaning, filter out ethanol, dry sediment at 45-50 DEG C,Obtain modification carboxy methylation bamboo shoots cellulose afterwards, be denoted as MBSC (ModifiedBambooSheetCellulose);
(10), after BSC is carried out to carboxymethyl-modification, need to prepare MBSC/ κ-Ka by inverse suspension crosslinking methodDraw glue composite aquogel pearl, first, the carboxy methylation bamboo shoots cellulose/κ-Ka after the modification of preparation 0.05-0.07 (g/ml)Draw glue composite solution 50-60ml, wherein the carboxy methylation bamboo shoots cellulose after modification and the mass ratio of kappa-carrageenan are 8:2-7:3, adds 2.5g-3g NaOH to carry out basification afterwards again and 6-10ml epoxychloropropane (ECH) is cross-linked, and treats itAfter stirring in magnetic agitation, carried out ultrasonic deaeration processing, ultrasonic power is 200W, and ultrasonic time 2min, obtainsMixture glue;
(11), after ultrasonic, 25ml-30ml mixture glue is splashed into rapidly to the just liquid in magnetic stirrerIn paraffin, and in dropping process, magnetic stirring apparatus keeps 1000-1200rpm to prevent glue automatic bonding in atoleine,After stable, regulating magnetic stirring apparatus rotating speed is 700-800rpm;
(12) at room temperature, under 700-800rpm, stir with constant speed, after reaction 36-48h, withdrawal liquid stoneWax, obtains hydrogel, uses deionized water and 85-95% ethanol respectively the hydrogel of preparing to be washed, and removes not anti-The crosslinking agent of having answered and reaction raw materials;
(13) hydrogel of preparing is put into-20 DEG C of refrigerator freezing 12-16h, put into and on freeze dryer, carry out freezing vacuumDry, obtain described modification bamboo shoots cellulose composite aquogel. Obtaining its diameter is 2-3mm, water white transparency, particle size distribution rangeAlso very narrow, be the MBSC/ kappa-carrageenan composite aquogel pearl of spheroidal particle completely, i.e. composite aquogel.
In above-mentioned method, described in step (1), bamboo shoots leftover bits and pieces refers to the aging fiber that bamboo shoots work in-process abandonsThe more discarded object that is unfavorable for processing is that the rear portion bamboo shoot root of bamboo shoots divides; The bamboo shoots leftover bits and pieces slag powder diameter obtaining is0.1-0.6mm。
In above-mentioned method, in step (2), the mass ratio of described bamboo shoots powder and sodium chlorite is 1:1-1:0.8, bleachingTime is 2-3h.
In above-mentioned method, in step (4), the mass percent concentration of described potassium hydroxide aqueous solution is 10%-15％。
In above-mentioned method, in step (4), the concrete grammar of described washing is: make to be successively washed with distilled water to filtratePH is neutral, uses afterwards the each washing of 95% ethanol and absolute ethyl alcohol 1 time.
In above-mentioned method, in step (6), in described reactor, should be provided with magnetic stirring apparatus and heated at constant temperature concussion dressPut.
In above-mentioned method, in step (6), in reaction system, the mass ratio of distilled water and isopropyl alcohol is 1:8.5-1:10.
In above-mentioned method, in step (7), the mass ratio of alkalization bamboo shoots cellulose and sodium chloroacetate is 1:1.2-1:1.4,Sodium chloroacetate is adding before reaction system, 1:1 predissolve in absolute ethyl alcohol in mass ratio.
In above-mentioned method, in step (9), the mode of washing of described ethanol washing is: use successively 75%, 85%,95% ethanol washs 3 times modified product.
In above-mentioned method, described in step (11), in reactor, the length of magnetic agitation rotor accounts for reactor bottom diameter75%-80%; Atoleine accounts for the 45%-55% of reactor volume.
A kind of bamboo shoots leftover bits and pieces is carried out to modification prepare composite aquogel and be applied to the dye of positive ion as sorbing material and divideAbsorption or the Thermosensitive Material Used for Controlled Releasing of Medicine of son.
Adsorbent of the present invention compared with prior art has following feature:
(1) adsorbent of the present invention primary raw material used is discarded bamboo shoots leftover bits and pieces slag, and source is abundant, cheap, inhalesAttached dose to dye molecule high adsorption capacity, and absorption property is stable;
(2) bamboo shoots cellulose only needs carboxy methylation one step modification, and modified technique is fairly simple;
(3) modification bamboo shoots cellulose is prepared in hydrogel process and is added appropriate carragheen, the composite aquogel of preparingMatter structure is improved;
(4) bamboo shoots cellulose, through after modification, is introduced carboxyl by carboxy methylation, carboxyl on hydrogel in the aqueous solutionIonize, produce the carboxylic ions of electronegative property, the dye of positive ion is had to good adsorption effect;
(5) hydrogel that prepared by the present invention can be for the absorption of the dye of positive ion, and the described dye of positive ion refers toIn the aqueous solution, group is with the dyestuff of positive charge, as: methylene blue, cationic red G etc.;
(6) taking methylene blue as drug model, similar to some medicines because of molecular structure, can select described in it studiesThe absorption of hydrogel and slowly-releasing behavior, for this hydrogel provides certain theoretical foundation as Thermosensitive Material Used for Controlled Releasing of Medicine.
(7) composite aquogel of the present invention adopts via Inverse-Phase Suspension Polymerization moulding, the hydrogel beads good looking appearance of formation, grainFootpath distribution homogeneous, specific area is large, and the oil phase liquid paraffin body using can be repeatedly used, and reduces cost and pollution.
(8) reaction condition gentleness, is used green non-pollution NaOH system to carry out hydrogel preparation, and process route is simple and easy toOK, be easy to industrialization operation.
Brief description of the drawings
MBSC and MBSC-CMC/CN-GELFTIR spectrogram in Fig. 1 embodiment 1;
Fig. 2 embodiment 2 Methylene Blue initial concentrations affect modification bamboo shoots cellulose composite aquogel adsorption capacity;
In Fig. 3 embodiment 3, initial pH affects modification bamboo shoots cellulose composite aquogel adsorption capacity.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described and description:
Embodiment 1:
(1) bamboo shoots leftover bits and pieces, through after washing, is dried after 12h in 70 DEG C, the shape that is cut into small pieces, and pulverizer was pulverized80 mesh sieves, obtain bamboo shoots ground-slag end, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:20,70 DEG C of conditionsUnder complete and process 2h passivation bamboo shoots active enzyme, the glacial acetic acid regulator solution pH that is 10% with mass fraction is afterwards 3.8,After adjusting, add sodium chlorite to carry out bleaching 2h, the quality of the addition of sodium chlorite and bamboo shoots leftover bits and pieces powderThan for 1:1, under 80 DEG C of conditions, carry out bleaching, to remove the lignin in bamboo shoots leftover bits and pieces;
(3) after bleaching, insoluble flocculent substance in filtering solution, and wash with distilled water that it is colourless to filtrate,Rear service property (quality) mark 90% ethanol carries out alcohol wash, is finally dried and processes 20h in 60 DEG C of baking ovens, obtains pretreatment bamboo shoots fibreDimension, is denoted as PBSC (PretreatmentBambooShootCellulose). Pretreatment bamboo shoots cellulose was pulverized 80 mesh sievesBeing carried out at mass fraction is the 16h that alkalizes in 10% potassium hydroxide solution, and wherein pretreatment bamboo shoots cellulose and potassium hydroxide are water-solubleThe amount ratio of liquid is 1:15 (g/ml), and it is neutral after alkalization, washing to filtrate with distilled water, then uses 95% ethanol to washAfter washing, dry 16h at 50 DEG C, obtains bamboo shoots cellulose after de-hemicellulose, is denoted as BSC (BambooShootCellulose)。
(4) after dried de-hemicellulose, after the pulverizing of bamboo shoots cellulose, cross 80 mesh sieves and carry out carboxymethyl-modification, modificationCondition is as follows: 10g bamboo shoots cellulose is added in 200ml aqueous isopropanol, the matter of distilled water and isopropyl alcohol in aqueous isopropanolAmount ratio is in 1:9, then adds successively 30% hydrogen peroxide, the 50%NaOH solution 16ml of 80ul, 2h basification.
(5) alkalize completely, add 50% sodium chloroacetate solution 14ml gradient increased temperature etherificate. Reaction condition: room temperature 30min,Shaking water bath 30min at 45 DEG C, shaking water bath 30min at 60 DEG C, processes 80min for last 75 DEG C.
(6) treat that it recovers room temperature, again add the 50%NaOH of 6ml to carry out double alkalisation 30min, carry out secondary temperature elevation etherChange, etherificate parameter is with etherificate is consistent for the first time.
(7), after etherificate, supernatant discarded, adds 300ml methyl alcohol room temperature concussion 30min, after filter liquor, again addsThe rear hold over night of concussion after 300ml methyl alcohol, regulating sample liquid with glacial acetic acid is the neutral rear rear supernatant discarded that leaves standstill that stirs, and makes successivelyEthanolic solution with 75%, 85%, 95% cleans 3 times precipitation successively, filters out ethanol after cleaning, dry at 50 DEG CDry, obtain modification carboxy methylation bamboo shoots cellulose afterwards.
(8) the carboxy methylation bamboo shoots cellulose/carragheen composite solution 50ml after the modification of preparation 0.07 (g/ml), itsCarboxy methylation bamboo shoots cellulose after middle modification and the mass ratio of carragheen are 7:3, add afterwards 2.5g NaOH to enter againRow basification and 8ml epoxychloropropane (ECH) are cross-linked, and after it stirs in magnetic agitation, 200W is ultrasonic de-Gas disposal 2min, obtains mixture glue.
(9) use dropper that 25ml mixture glue is just splashed into rapidly in agitated liquid paraffin, dropping process keeps magneticPower stirs 1000rpm, and after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, the length of magnetic agitation rotor in reactorDegree accounts for 75% of reactor bottom diameter, and atoleine accounts for 50% of reactor volume.
(10) reactant, after atoleine reaction 36h, reclaims the atoleine in beaker, uses deionized water and 95%Ethanol washs the hydrogel of preparing, and can obtain its diameter probably at 2.4mm left and right, water white transparency, particle diameter distribution modelEnclosing also very narrowly, is spheroidal particle carboxymethyl bamboo shoots cellulose/carragheen composite aquogel pearl completely.
(11) will prepare described hydrogel beads and put into-20 DEG C of refrigerators and carry out freezing 12h, 12h is processed in freeze drying afterwards,Obtain described composite aquogel.
Get carboxy methylation bamboo shoots cellulose (being denoted as: MBSC) and the carboxy methylation bamboo shoots fibre in appropriate embodiment 1, preparedTie up plain composite aquogel (be denoted as: MBSC-CMC/CN-GEL, wherein CN refers to kappa-carrageenan), with KBr (spectroscopic pure) compressing tablet, thenWith FT-IR infrared spectrum (BrukerVector33, German) in 4000-400cm-1Under scan, can obtain sample F T-IR spectrogram, as shown in Fig. 1 in brief description of the drawings.
Analyzed by Fig. 1, in MBSC, find at 1416cm-1And 1602cm-1The absworption peak of position is mainly because carboxyl entersRow symmetry and asymmetric vibrations cause, at 1060cm-1Place is the distinctive flexible shock absorbing of acetal radical peak, and these are carboxymethylsDistinctive group, proves that carboxymethyl is successfully connected on bamboo shoots cellulose and can finds in MBSC-CMC/CN-GEL1377cm-1,1323cm-1And 1246cm-1There is new peak in place, they are because MBSC is under the crosslinked action of epoxychloropropaneForm-CH-O-CH-ehter bond stretching peak, this proves modification bamboo shoots carboxymethyl cellulose and epoxychloropropane generation cross-linking reaction.In addition, at 847cm-1The new peak that place occurs is-the flexible vibrations of C-O-S-that this proves have carragheen to become in described composite aquogelPoint, composite aquogel preparation is successful.
Embodiment 2:
(1) bamboo shoots leftover bits and pieces, through after washing, is dried after 16h in 80 DEG C, the shape that is cut into small pieces, and pulverizer was pulverized80 mesh sieves, obtain bamboo shoots ground-slag end, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:25,65 DEG C of conditionsUnder complete and process 2.5h passivation bamboo shoots active enzyme, the glacial acetic acid regulator solution pH that is 10% with mass fraction afterwards exists4.0, after adjusting, add sodium chlorite to carry out bleaching 2h, the addition of sodium chlorite and bamboo shoots leftover bits and pieces powderMass ratio is 0.9:1, under 80 DEG C of conditions, carries out bleaching, to remove the lignin in bamboo shoots leftover bits and pieces.
(3) after bleaching, insoluble flocculent substance in filtering solution, and wash with distilled water that it is colourless to filtrate,Rear service property (quality) mark 90% ethanol carries out alcohol wash, is finally dried and processes 20h in 50 DEG C of baking ovens, obtains pretreatment bamboo shoots fibreDimension. Pretreatment bamboo shoots cellulose was pulverized 80 mesh sieves, and to be carried out at mass fraction be the 18h that alkalizes in 10% potassium hydroxide solution, whereinThe solid-liquid ratio of pretreatment bamboo shoots cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), after alkalization, washs extremely with distilled waterFiltrate is neutral, then uses after 95% ethanol washing, and dry 16h at 50 DEG C, obtains bamboo shoots cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots cellulose carries out carboxy methylation according to method in embodiment 1 after pulverizingModification, finally obtains modification carboxy methylation bamboo shoots cellulose afterwards.
(5) the carboxy methylation bamboo shoots cellulose/carragheen composite solution 50ml after the modification of preparation 0.07 (g/ml), itsCarboxy methylation bamboo shoots cellulose after middle modification and the mass ratio of carragheen are 7:3, add afterwards 3g NaOH to carry out againBasification and 10ml epoxychloropropane (ECH) are cross-linked, after it stirs in magnetic agitation, and 200W ultrasonic degasProcess 2min, obtain mixture glue.
(6) use dropper that 25ml mixture glue is just splashed into rapidly in agitated liquid paraffin, dropping process keeps magneticPower stirs 1000rpm, and after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, the length of magnetic agitation rotor in reactorDegree accounts for 75% of reactor bottom diameter; Atoleine accounts for 50% of reactor volume.
(7) reactant, after atoleine reaction 36h, reclaims the atoleine in beaker, uses deionized water and 95%Ethanol washs the hydrogel of preparing, and can obtain its diameter probably at 2.4mm left and right, water white transparency, particle diameter distribution modelEnclosing also very narrowly, is spheroidal particle carboxymethyl bamboo shoots cellulose/carragheen composite aquogel pearl completely.
(8) will prepare described hydrogel beads and put into-20 DEG C of refrigerators and carry out freezing 12h, 12h is processed in freeze drying afterwards,Obtain described composite aquogel.
The neutral methylene blue solution of configuration variable concentrations, then pipettes variable concentrations methylene blue solution with pipette25ml is in clear bottle, and concussion 30s mediates. Then in each serum bottle, pour accurate load weighted 0.03g freeze drying water-setting intoGlue, leaves standstill 5d.
By adsorption capacity computing formula:And Rm＝(1-Ct/C0Described water-setting is calculated in) × 100Glue adsorption capacity and adsorption efficiency, wherein Q is adsorption capacity, unit is mg/g; RmFor adsorption efficiency; C0, Ct is at initial timeSimulation solution concentration with the t moment; V is simulation liquor capacity, and unit is ml; M is adsorbent mass g.
Methylene blue initial concentration affects as shown in Figure 2 described hydrogel adsorption capacity.
As seen from Figure 2, along with the increase of methylene blue solution initial concentration, bamboo shoots carboxymethyl cellulose/carragheenComposite aquogel is ever-increasing to its adsorption capacity, but adsorption efficiency declining, and is 1200mg/L place at initial concentrationAdsorption capacity can reach 665.43mg/g, and adsorption efficiency reaches 55.48%. Composite aquogel has so large to methylene blueAdsorption capacity is mainly because have a large amount of carboxylic acid ions above bamboo shoots carboxymethyl cellulose after modification, together with the sulphur on carragheenThe negative electrical charge that acid ion is entrained, has to the dye of positive ion that very strong adsorption capacity causes.
Embodiment 3:
(1) bamboo shoots leftover bits and pieces, through after washing, is dried after 16h in 75 DEG C, the shape that is cut into small pieces, and pulverizer was pulverized80 mesh sieves, obtain bamboo shoots ground-slag end, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to the ratio of material-water ratio 1:20, under 70 DEG C of conditions, killsThe blue or green 2h passivation bamboo shoots active enzyme of processing, uses 10% glacial acetic acid regulator solution pH 3.8 afterwards, after adjusting, adds AsiaSodium chlorate carries out bleaching 3h, and the mass ratio of the addition of sodium chlorite and bamboo shoots leftover bits and pieces powder is 1:1, under 80 DEG C of conditionsCarry out bleaching, to remove the lignin in bamboo shoots leftover bits and pieces.
(3) after bleaching, insoluble flocculent substance in filtering solution, and wash with distilled water that it is colourless to filtrate,Rear service property (quality) mark 95% ethanol carries out alcohol wash, is finally dried and processes 20h in 50 DEG C of baking ovens, obtains pretreatment bamboo shoots fibreDimension. Pretreatment bamboo shoots cellulose was pulverized 80 mesh sieves, and to be carried out at mass fraction be the 18h that alkalizes in 10% potassium hydroxide solution, whereinThe solid-liquid ratio of pretreatment bamboo shoots cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), after alkalization, washs extremely with distilled waterFiltrate is neutral, then uses after 95% ethanol washing, and dry 16h at 50 DEG C, obtains bamboo shoots cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots cellulose carries out carboxy methylation according to method in embodiment 1 after pulverizingModification, finally obtains modification carboxy methylation bamboo shoots cellulose afterwards.
(5) the carboxy methylation bamboo shoots cellulose/carragheen composite solution 50ml after the modification of preparation 0.06 (g/ml), itsCarboxy methylation bamboo shoots cellulose after middle modification and the mass ratio of carragheen are 7:3, add afterwards 2.5g NaOH to enter againRow basification and 10ml epoxychloropropane (ECH) are cross-linked, after it stirs in magnetic agitation, and ultrasonic degas placeReason, obtains mixture glue.
(6) use dropper that mixture glue is just splashed into rapidly in agitated liquid paraffin, dropping process keeps magnetic force to stirMix 1200rpm, after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, and in reactor, the length of magnetic agitation rotor accounts for80% of reactor bottom diameter; Atoleine accounts for 55% of reactor volume.
(6) reactant, after atoleine reaction 36h, uses deionized water and 95% ethanol to enter the hydrogel of preparingRow washing, can obtain spheroidal particle carboxymethyl bamboo shoots cellulose/carragheen composite aquogel pearl.
(7) will prepare described hydrogel beads and put into-20 DEG C of refrigerators and carry out freezing 12h, 12h is processed in freeze drying afterwards,Obtain described composite aquogel.
Configure the methylene blue solution of different pH values, then with pipette pipette variable concentrations methylene blue solution 25ml inIn small beaker. Then in each small beaker, pour accurate load weighted 0.025g freeze drying hydrogel into, leave standstill 5d.
By adsorption capacity computing formula:And Rm＝(1-Ct/C0Described water-setting is evaluated in) × 100Glue adsorption capacity and adsorption efficiency, wherein Q is adsorption capacity, unit is mg/g; RmFor adsorption efficiency; C0, Ct is at initial timeSimulation solution concentration with the t moment; V is simulation liquor capacity, and unit is ml; M is adsorbent mass g.
Methylene blue initial concentration affects as shown in Figure 2 described hydrogel adsorption capacity.
As seen from Figure 3, along with the increase of solution initial pH value, bamboo shoots carboxymethyl cellulose/carragheen compound water congealingGlue is ever-increasing to methylene blue adsorption number ability, and adsorption efficiency is also increasing, and is the adsorption capacity energy at 9.0 places at initial pHReach 408.73mg/g, adsorption efficiency reaches 82.87%.
Embodiment 4:
(1) bamboo shoots leftover bits and pieces, through after washing, is dried after 12h in 80 DEG C, the shape that is cut into small pieces, and pulverizer was pulverized80 mesh sieves, obtain bamboo shoots ground-slag end, and its powder diameter is 0.1-0.6mm.
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to the ratio of material-water ratio (mass ratio) 1:20,75 DEG C of conditionsUnder complete and process 2h passivation bamboo shoots active enzyme, the glacial acetic acid regulator solution pH that is 10% with mass fraction is afterwards 4.0,After adjusting, add sodium chlorite to carry out bleaching 3h, the quality of the addition of sodium chlorite and bamboo shoots leftover bits and pieces powderThan for 1:1, under 80 DEG C of conditions, carry out bleaching, to remove the lignin in bamboo shoots leftover bits and pieces.
(3) after bleaching, filter insoluble flocculent substance, and wash with distilled water that it is colourless to filtrate, finally useMass fraction is that 90% ethanol carries out alcohol wash, is finally dried and processes 18h in 50 DEG C of baking ovens, obtains pretreatment bamboo shoots fiber.Pretreatment bamboo shoots cellulose was pulverized 80 mesh sieves and is carried out at mass fraction and is the 18h that alkalizes in 10% potassium hydroxide solution, wherein pre-The solid-liquid ratio of processing bamboo shoots cellulose and potassium hydroxide aqueous solution is 1:15 (g/ml), after alkalization, washs to filter with distilled waterLiquid is neutral, then uses after 95% ethanol washing, and dry 16h at 50 DEG C, obtains bamboo shoots cellulose after de-hemicellulose.
(4) after dried de-hemicellulose, bamboo shoots cellulose carries out carboxy methylation according to method in embodiment 1 after pulverizingModification, finally obtains modification carboxy methylation bamboo shoots cellulose afterwards.
(5) the carboxy methylation bamboo shoots cellulose/carragheen composite solution 50ml after the modification of preparation 0.06 (g/ml), itsCarboxy methylation bamboo shoots cellulose after middle modification and the mass ratio of carragheen are 7:3, add afterwards 2.5g NaOH to enter againRow basification and 10ml epoxychloropropane (ECH) are cross-linked, and after it stirs in magnetic agitation, 200W is ultrasonic de-Gas disposal 2min, obtains mixture glue.
(6) use dropper that 25ml mixture glue is just splashed into rapidly in agitated liquid paraffin, dropping process keeps magneticPower stirs 1000rpm, and after dropwising, regulating magnetic stirring apparatus rotating speed is 800rpm, the length of magnetic agitation rotor in reactorDegree accounts for 80% of reactor bottom diameter; Atoleine accounts for 50% of reactor volume.
(7) reactant, after atoleine reaction 48h, uses deionized water and 95% ethanol to enter the hydrogel of preparingRow washing, can obtain spheroidal particle carboxymethyl bamboo shoots cellulose/carragheen composite aquogel.
(8) will prepare described hydrogel beads and put into-20 DEG C of refrigerators and carry out freezing 12h, 12h is processed in freeze drying afterwards,Obtain described composite aquogel.
Configuration concentration be the methylene blue solution of 50mg/L in beaker, then accurately load weighted to adding in beakerDescribed in 0.300g, hydrogel, in this beaker, leaves standstill 72h, and described hydrogel can pass through embodiment 2 to the absorption of methylene blueThe calculation of capacity formula of middle step (10) draws. Be under 50mg/L condition by calculating at methylene blue initial concentration,The adsorption capacity of described hydrogel is 166.65mg/g, and adsorption efficiency is 99.94%.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not to the present inventionThe restriction of embodiment. For those of ordinary skill in the field, can also make on the basis of the above descriptionThe variation that other is multi-form or variation. Here without also giving exhaustive to all embodiments. All of the present inventionAny amendment of doing within spirit and principle, be equal to replacement and improvement etc., all should be included in the protection of the claims in the present inventionWithin scope.
Claims (10)
1. bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that, described composite aquogelExtract after cellulose and carry out after modification with sodium chloroacetate by bamboo shoots leftover bits and pieces, then it is crosslinked, anti-phase outstanding afterwards to carry out epoxychloropropaneFloating polymerization, finally carries out freeze drying and forms, and concrete steps are:
(1) bamboo shoots leftover bits and pieces is through washing, oven drying 12-16h, and baking temperature is 70-80 DEG C or dries in the sun, dryThe shape that is cut into small pieces afterwards, pulverized 80 mesh sieves through pulverizer afterwards, obtained bamboo shoots ground-slag end for subsequent use;
(2) bamboo shoots leftover bits and pieces ground-slag end adds distilled water according to material water quality than the ratio of 1:20-1:25,65-80 DEG C of conditionUnder complete and process 2h-2.5h passivation bamboo shoots active enzyme, use afterwards the glacial acetic acid regulator solution pH of mass fraction 10%-15%At 3.8-4.0, after adjusting, add sodium chlorite to carry out bleaching, under 75-80 DEG C of condition, carry out bleaching, withRemove the lignin in bamboo shoots leftover bits and pieces;
(3) after bleaching, filtering solution, get insoluble flocculent substance, and it is colourless to be washed with distilled water to filtrate, finally usesMass fraction 85%-95% ethanol carries out alcohol wash, is finally dried and processes 16-20h in 50-70 DEG C of baking oven, obtains pretreatment bambooBamboo shoot fiber;
(4) dry pretreatment bamboo shoots fiber is later pulverized, crossed 80 mesh sieves, according to solid-liquid ratio, 1:15-1:20g/ml addsEnter to potassium hydroxide aqueous solution and stir alkalization 12h-20h, washing, puts into baking oven and process 16-20h at 50-70 DEG C, dry obtainingBamboo shoots cellulose after de-hemicellulose;
(5) bamboo shoots cellulose after dry de-hemicellulose is pulverized, after pulverizing, crossed 80 mesh sieves;
(6) modified technique is as follows: accurately weigh bamboo shoots cellulose after the de-hemicellulose that 10-12g step (5) obtains, add anti-Answer in device, add afterwards distilled water and isopropyl alcohol, then after adding the mass fraction of 80-100 μ l to be 30%-35% hydrogen peroxide, carry outShake up, after shaking up, adding mass fraction is 40%-50%NaOH solution 16-20ml, carries out basification, and alkalization time is 2-3h, bamboo shoots cellulose obtains alkalizing;
(7) the modification stage adds sodium chloroacetate solution in alkalization bamboo shoots cellulose, starts gradient increased temperature etherificate, and reactant liquor existsUnder magnetic agitation condition, in room temperature treatment 30-50min, be transferred to afterwards shaking table and carry out 40-45 DEG C of shaking water bath 30-40min, itAfter carry out 55-60 DEG C of shaking water bath 30-40min, then carry out 75-80 DEG C of high-temperature process 80-90min;
(8) recover after completion of the reaction room temperature, again adding 6ml mass fraction is that 50%NaOH solution carries out double alkalisation, when alkalizationBetween be 30min, after alkalization, carry out secondary etherificate, etherificate concrete technology and temperature parameter are with consistent in (7);
(9), after treating etherificate, supernatant discarded after cool to room temperature is poured 300-500ml into after the spherical dope of lower floor is coolingMethyl alcohol processing, shaking table room temperature concussion 30-40min, outwells upper strata alcohol liquid after stratification, again add after 300-500ml methyl alcoholAfter shaking, after hold over night, be adjusted to rear the leaving standstill of neutral rear stirring with glacial acetic acid and outwell upper strata alcohol liquid, carry out ethanol washing, cleanAfter filter out ethanol, dry sediment at 45-50 DEG C, obtains the carboxy methylation bamboo shoots cellulose after modification;
(10) prepare the technique of modification bamboo shoots cellulose/kappa-carrageenan composite aquogel pearl: the modification of preparation 0.05-0.07g/mlCarboxy methylation bamboo shoots cellulose/kappa-carrageenan composite solution 50-60ml afterwards, wherein the carboxy methylation bamboo shoots after modificationThe mass ratio of cellulose and kappa-carrageenan is 8:2-7:3, adds afterwards 2.5g-3g NaOH to carry out basification and 6-again10ml epoxychloropropane (ECH) is cross-linked, and after it stirs in magnetic agitation, is carried out ultrasonic deaeration processing,Obtain mixture glue;
(11), after ultrasonic, 25ml-30ml mixture glue is splashed into rapidly to the just liquid that is equipped with in magnetic stirrerIn the reactor of paraffin, and in dropping process magnetic stirring apparatus keep 1000-1200rpm prevent glue in atoleine fromMoving bonding, after stable, regulating magnetic stirring apparatus rotating speed is 700-800rpm;
(12) at room temperature, under 700-800rpm, stir with constant speed, after reaction 36-48h, withdrawal liquid paraffin,Obtain hydrogel, use deionized water and 85-95% ethanol respectively the hydrogel of preparing to be washed, remove unreacted completeCrosslinking agent and reaction raw materials;
(13) hydrogel of preparing is put into refrigerator freezing 12-16h, put on freeze dryer and carry out vacuum freezedrying, obtainDescribed modification bamboo shoots cellulose composite aquogel, obtaining its diameter is 2-3mm, water white modification bamboo shoots cellulose/κ-KaDraw glue composite aquogel pearl, i.e. composite aquogel.
2. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,Bamboo shoots leftover bits and pieces described in step (1) refers to that aging fiber that bamboo shoots work in-process abandons is more and is unfavorable for the discarded of processingThing is that the rear portion bamboo shoot root of bamboo shoots divides; The bamboo shoots leftover bits and pieces slag powder diameter obtaining is 0.1-0.6mm.
3. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (2), the mass ratio of described bamboo shoots powder and sodium chlorite is 1:1-1:0.8, and bleaching time is 2-3h.
4. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (4), the mass percent concentration of described potassium hydroxide aqueous solution is 10%-15%.
5. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (4), the concrete grammar of described washing is: make to be successively washed with distilled water to filtrate pH for neutral, use afterwards 95% secondThe each washing of alcohol and absolute ethyl alcohol 1 time.
6. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (6), in described reactor, should be provided with magnetic stirring apparatus and heated at constant temperature rocking equipment; In reaction system distilled water withThe mass ratio of isopropyl alcohol is 1:8.5-1:10.
7. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (7), the mass ratio of alkalization bamboo shoots cellulose and sodium chloroacetate is 1:1.2-1:1.4, and sodium chloroacetate is adding reaction systemBefore, 1:1 predissolve in absolute ethyl alcohol in mass ratio.
8. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,In step (9), the mode of washing of described ethanol washing is: use successively 75%, 85%, 95% ethanol to wash 3 to modified productInferior.
9. according to claim 1 bamboo shoots leftover bits and pieces is carried out to the method that composite aquogel is prepared in modification, it is characterized in that,Described in step (11), in reactor, the length of magnetic agitation rotor accounts for the 75%-80% of reactor bottom diameter; Atoleine accounts forThe 45%-55% of reactor volume.
10. the composite aquogel that the described preparation method of one of claim 1-9 prepares as sorbing material be applied to sun fromIn the absorption or Thermosensitive Material Used for Controlled Releasing of Medicine of sub-dye molecule.
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| CN104387618B (en) * | 2014-10-30 | 2016-07-06 | 昆明理工大学 | A kind of preparation method of the derivative blended gel of leaf of Semen Maydis holocellulose |
| CN105131317B (en) * | 2015-09-17 | 2018-06-29 | 华南理工大学 | Compound water congealing glued membrane and bamboo shoots leftover bits and pieces prepare method and the application of the aquagel membrane |
| CN105111466A (en) * | 2015-09-17 | 2015-12-02 | 华南理工大学 | Environmentally-sensitive hydrogel and method and application for preparing hydrogel by using bamboo shoot scraps |
| CN105457604B (en) * | 2015-11-30 | 2018-02-09 | 同济大学 | A kind of preparation method of the sorbing material based on natural polysaccharide |
| CN105435751B (en) * | 2016-01-06 | 2017-10-27 | 昆明理工大学 | A kind of preparation method of cornstalk core regenerated polysaccharides etherate plural gel |
| CN106589411B (en) * | 2016-11-28 | 2019-05-14 | 华南理工大学 | A kind of pineapple bran carboxymethyl cellulose/polyvinyl alcohol/mesoporous silicon oxide composite hydrogel and the preparation method and application thereof |
| CN107987323B (en) * | 2017-11-13 | 2020-07-28 | 华南理工大学 | Slow-release aerogel and indometacin-loaded slow-release aerogel |
| CN110523390B (en) * | 2019-08-23 | 2021-08-10 | 华南理工大学 | Coffee residue adsorbent with hydrophobicity and preparation method thereof |
| US20220111360A1 (en) * | 2019-09-25 | 2022-04-14 | Fu Zhou University | A method for preparing a catalyst for inferior residual oil suspended bed hydrocracking |
| CN112521627B (en) * | 2020-10-14 | 2022-05-03 | 浙江树人学院（浙江树人大学） | Preparation method of green composite hydrogel with slow-release type purification and sterilization functions |
| CN112663381A (en) * | 2020-12-09 | 2021-04-16 | 武汉纺织大学 | Preparation method of bamboo shoot shell cellulose nanowhisker |
| CN112852003B (en) * | 2021-03-16 | 2022-04-12 | 浙江大学 | Method for preparing cellulose/sodium alginate composite aerogel from bamboo shoot leftovers, product and application |
| CN112920332B (en) * | 2021-03-18 | 2023-03-10 | 河南工程学院 | Method for preparing green hydrogel by crosslinking of various wastes |
| CN113150324B (en) * | 2021-04-13 | 2023-02-14 | 华南理工大学 | TEMPO oxidized Millettia speciosa champ cellulose/gellan gum pH response type hydrogel and preparation method and application thereof |
| CN114456008A (en) * | 2022-02-25 | 2022-05-10 | 峰景园林工程集团有限公司 | Modifying agent for improving tree transplanting survival rate and preparation method thereof |
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