CN103508508A - Application of porous biomass resin in adsorptive separation - Google Patents
Application of porous biomass resin in adsorptive separation Download PDFInfo
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- CN103508508A CN103508508A CN201210222311.3A CN201210222311A CN103508508A CN 103508508 A CN103508508 A CN 103508508A CN 201210222311 A CN201210222311 A CN 201210222311A CN 103508508 A CN103508508 A CN 103508508A
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Abstract
The invention relates to a porous biomass resin and application thereof in adsorptive separation. The biomass resin containing multiple surface oxygen-containing groups such as sulfonic groups, carboxyl groups, hydroxyl groups and the like is mainly used for adsorptive separation of dyes and metal ions in wastewater. Through the combined actions of ion exchange, physical adsorption, complexing, pore canal effect and the like, the resin can adsorb multiple dyes and metal ions; and the removal rate can be up to 90% or above.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of multiporous biological matter resin and the application in fractionation by adsorption thereof.
Background technology
Waste water from dyestuff and the harm of toxic heavy metal Wastewater on Ecological Environmental are very large.After toxic wastewater entered environment, be difficult to be biodegradable, poisonous element accumulates in vivo by food chain, destroys organism normal physiological Metabolic activity, is detrimental to health.The conventional treatment process of waste water has the methods such as the precipitator method, electrolytic process, reduction method, extraction process, ion exchange method, absorption.
Absorption method is carried out water treatment, because it is applied widely, good, the recyclable useful material for the treatment of effect and the advantage such as sorbent material is reusable, has been widely used in the fields such as chemical industry, environment protection, medical and health and biotechnology.Along with constantly improving of existing performance of the adsorbent and succeeding in developing of new adsorbent, the application prospect of absorption method in water treatment is more wide.
At present, the Nonrenewable resources such as oil are increasingly exhausted, and people have turned one's attention to renewable resources.Xylogen is the Main By product of wood saccharification industry and pulp and paper industry, if be not fully utilized, serious environment pollution not only, also can cause the significant waste of resource.In recent years, people pass through the controlled chemically modified of lignin structure (sulfuration, sulfomethylation, methylolation, grafting, condensation etc.), improve its chemical reactivity or control its aggregated structure and interaction force intensity, strengthen its surfactivity, to improve its absorption property.
Acid system paper-making pulping process can produce a large amount of sulfonated lignin.In order rationally to utilize, minimizing threatens to environment, take sulfonated lignin as body material, the solid lignin adsorbing material of synthesizing new environmental protection in eco-friendly chemical mediator, separation for heavy metal ion, the processing of waste water from dyestuff, thus reach the object of the treatment of wastes with processes of wastes against one another, be conducive to the effectively separated of sorbing material and waste water simultaneously.
Document (New Chemical Materials, 2009,39, (7): 68-72) adopting sodium lignosulfonate is raw material, utilizes inverse suspension polymerization technology, has prepared lignin-base resin.And studied it to heavy metal ion Pb
2+, Cd
2+absorption property.Document (ion-exchange and absorption, 2006,22(3): 231-236) take calcium lignin sulphonate as raw material, under acidic conditions, take formaldehyde as linking agent, whiteruss is organic phase, by inverse suspension polymerization, prepare the controlled Spherical Lignin group ion exchange resin of particle diameter, studied them to Cr
3+absorption property.It is raw material that document (Chinese papermaking journal, 2005,20(1) 111-113) adopts calcium lignosulfonate and formaldehyde, utilize inverse suspension polymerization technology, using whiteruss and a small amount of tensio-active agent as organic phase, prepare spherical lignin base ion exchange resin, and studied resin to Cr
3+and Cr
2o
7 2-characterization of adsorption.It is raw material that document (Environmental science and technology, 2009,32(1) 71-74) be take sodium lignosulfonate and formaldehyde, and whiteruss is organic phase, and tensio-active agent is dispersion agent, temperature programming heating, and sample, through pre-treatment, obtains solid lignin adsorbing material.Investigated its cationic dyestuff methylene blue adsorption number performance.
The current material for dye adsorption and separation of heavy metal ions, major part be take biomass as the preparation of raw material employing inverse suspension polymerization technology, need to add certain dispersion agent, tensio-active agent, also need strictly to control the consumption of stir speed (S.S.) and dispersion agent, to guarantee the adsorption effect of resin.After separation, also to recycle to organic phases such as dispersion agent, tensio-active agents complex process.Adding of organic phase, increased again cost.
Therefore, with the low circuit of simple preparation technology, environmental friendliness and cost, develop a kind of biomass resin having compared with high absorption property, and can realize the object of the treatment of wastes with processes of wastes against one another, become the focus that researchist pays close attention to.
Summary of the invention
The object of the present invention is to provide a kind of method of wastewater treatment, emphasis is the preparation for the sorbent material multiporous biological matter resin of wastewater treatment.This resin be take in acid system paper-making pulping process and is produced a large amount of sulfonated lignin as raw material, need not add the organic solvents such as dispersion agent and tensio-active agent, under the controlled reaction conditions of gentleness, by environmental friendliness circuit combination, there is the kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyl.Use it for the fractionation by adsorption of multiple dyestuff and heavy metal, realized the object of the treatment of wastes with processes of wastes against one another.
For achieving the above object, the present invention is by the following technical solutions:
The preparation of described catalyzer, by following processing step, complete: certain density lignosulfonic acid salt brine solution, aldehyde compound, template and catalyzer are joined in reaction vessel with certain proportion, mix, at the temperature of 50 ° of C～220 ° C, after reaction 2h～120h, dry, grind, under hydrofluoric acid room temperature, process 12h and remove above template, after 1M sulfuric acid acid treatment 2h, washing, to neutral, makes this material after oven dry.Absorption by this resin for dye well metal ion, clearance can reach more than 90%.Clearance=(C
o-C
e)/C
o* 100%.; C
oand C
ebe respectively the concentration of absorption front and back effects of ion.
The concrete implementation step of this resin static equilibrium absorption is:
Getting starting point concentration is 5mgL
-1～3000mgL
-1dye solution or starting point concentration are 5mgL
-1～2000mgL
-1heavy metal ion solution 100mL in Erlenmeyer flask, get this resin material of 1g in wherein, vibration for some time, centrifugation, measures the concentration of clear liquid, investigates the clearance of ion.Adsorption temp is 5 ° of C～50 ° C, and adsorption time is 5min～300min.Applicable dyestuff is basic dyestuff, dispersed dye, matching stain, reactive dyestuffs, substantive dyestuff etc.; Applicable heavy metal ion is Pb
2+, Cd
2+, Cu
2+, Zn
2+, Cr
3+deng.
The concrete implementation step of this resin dynamic adsorption is:
This resin material is packed into internal diameter certain, post length-to-diameter ratio is more than or equal to 1 pillar, and certain density dye solution or heavy metal ion solution are introduced in packed column under gravity or pressure-acting, after this material of flowing through, collect the clear liquid of water outlet, measure concentration, investigate the clearance of ion.Preferably length-to-diameter ratio is 2 ~ 50.Best ratio is 5 ~ 25.Applicable dyestuff is basic dyestuff, dispersed dye, matching stain, reactive dyestuffs, substantive dyestuff etc.; Applicable heavy metal ion is Pb
2+, Cd
2+, Cu
2+, Zn
2+, Cr
3+deng.Dye solution starting point concentration is 5mgL
-1～3000mgL
-1, heavy metal ion initial concentration solution 5mgL
-1～2000mgL
-1.Adsorption temp is 5 ° of C～60 ° C.
The absorption of ion is chemisorption and the coefficient result of physical adsorption normally, and need to have adsorption site.There is sulfonic group, carboxyl and hydroxyl kinds of surface oxy radical in the biomass resin that adopts aforesaid method to prepare, these functional groups can be used as the adsorption site of dye well metal ion.Oxy radical is by hydrogen bond, and the bonding actions such as sat linkage produce sequestering action to ion, generates lignin-base resin-metal chelate, shows the adsorptivity to metal ion.Ion-exchange also has certain effect aspect absorption, and strongly-acid oxy radical can be replaced with dyestuff or metal ion.Vesicular structure can cause duct effect, thus dyestuff or the metal ion of absorption corresponding size.Ion-exchange, physical adsorption, complexing and duct effect comprehensive action, make this resin have the stronger adsorptive power to dyestuff and heavy metal ion.
The adsorption rate that temperature is mainly reflected in early stage to the impact of adsorption effect is different.Resin is thermo-negative reaction to the absorption of ion, heats up and is conducive to chemisorption.Temperature is higher, and early stage, rate of adsorption was faster, and along with the prolongation of time, the chemisorption site in resin is progressively occupied by ion, and resin surface adsorbate is tending towards saturated, and temperature is more and more less on the impact of adsorption rate.Therefore,, in dynamic adsorption, in certain temperature range, when adsorption temp is higher, resin has good adsorption effect to waste water from dyestuff.
In the high solion of starting point concentration, the adsorptive capacity of resin is also high, and adsorptive capacity increases along with the rising of ionic concn; But when ionic concn is too high, loading capacity is tending towards saturated along with the continuous rising of concentration of metal ions, and adsorption rate declines thereupon.
In dynamic adsorption, suitable length-to-diameter ratio is to realize the important parameter of high-level efficiency separation.In the larger situation of length-to-diameter ratio, fractionation by adsorption is effective, but Pressure Drop is larger, and resistance to flow is large, the requirement in the life-span of the requirement of granule strength and adsorbate is improved, simultaneously also corresponding reduction of adsorption efficiency; Major diameter is smaller, fractionation by adsorption heterodyne.
The present invention compares with traditional sorbing material, has following several advantage:
1. raw material sources of the present invention are abundant, and reaction conditions is gentle, does not need to add the organic solvents such as dispersion agent and tensio-active agent, and cost is low, and preparation technology is simple.
2. the present invention is usingd the kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyl as adsorption site, can realize the fractionation by adsorption to dye well heavy metal ion by actings in conjunction such as ion-exchange, physical adsorption, complexing action and duct effects.
3. aspect fractionation by adsorption, there is universality, be applicable to basic dyestuff, dispersed dye, matching stain, reactive dyestuffs, the dyestuffs such as substantive dyestuff and Pb
2+, Cd
2+, Cu
2+, Zn
2+, Cr
3+etc. the absorption of contents of many kinds of heavy metal ion, and have the advantages that clearance is high.
Accompanying drawing explanation:
Fig. 1 is static equilibrium absorption and running balance absorption schematic diagram.The absorption of A static equilibrium, B dynamic adsorption.
Fig. 2 is in static equilibrium absorption, the relation of the clearance of Methylene Blue Ion and adsorption time and temperature.
Embodiment:
The following example will further describe the present invention, but content of the present invention is not limited to this.
Embodiment 1
Take magnesium lignosulfonate 50g, be made into mass concentration and be 30% the aqueous solution, 35g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 5gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 12g, stir until solution mixes, airtight, be placed in 100 ° of C baking ovens and react 24h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee magnesium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.Absorption by the resin of above-mentioned preparation for methylene blue.Take the above-mentioned resin of 1g, add the methylene blue solution 100mL of 1000mg/L, in 30 ℃ of constant temperature water bath vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 2
Take sodium lignosulfonate 50g, be made into mass concentration and be 30% the aqueous solution, 30g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 5gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 15g, stir until solution mixes, airtight, be placed in 100 ° of C baking ovens and react 24h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee sodium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.Absorption by the resin of above-mentioned preparation for methylene blue.Take the above-mentioned resin of 1g, add the methylene blue solution 100mL of 2500mg/L, in 30 ℃ of constant temperature water bath vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 3
Absorption by the resin of embodiment 2 preparations for methylene blue.Take the above-mentioned resin of 1g, add the methylene blue solution 100mL of 100mg/L, in 30 ℃ of constant temperature water bath vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid, the clearance of methylene blue is in Table 1.
Embodiment 4
Absorption by the resin of embodiment 2 preparations for methylene blue.Take the above-mentioned resin of 1g, add the methylene blue solution 100mL of 100mg/L, in 30 ℃ of constant temperature water bath vibration 30min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 5(dynamic adsorption)
Absorption by the resin of embodiment 2 preparations for methylene blue.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 10, under 30 ℃, pump function, introduces packed column by the methylene blue solution of the 2500mg/L of 100mL, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.The clearance of methylene blue is in Table 1.
Embodiment 6(dynamic adsorption)
Absorption by the resin of embodiment 2 preparations for methylene blue.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 20, under 30 ℃, pump function, introduces packed column by the methylene blue solution of the 2500mg/L of 100mL, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.The clearance of methylene blue is in Table 1.
Embodiment 7
Take sodium lignosulfonate 50g, be made into mass concentration and be 5% the aqueous solution, 15g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 30g silicon sol as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 15g, stir until solution mixes, airtight, be placed in 100 ° of C baking ovens and react 24h.Then the black material of preparation is dried at 110 ° of C, grind, remove template, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee sodium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for to Pb
2+absorption.Take the above-mentioned resin of 1g, add the Pb of 800mg/L
2+solution 100mL, in 25 ℃ of constant temperature water bath vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb
2+clearance in Table 1.
Embodiment 8
Take sodium lignosulfonate 50g, be made into mass concentration and be 5% the aqueous solution, 25g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 30g silicon sol as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 12g, stir until solution mixes, airtight, be placed in 100 ° of C baking ovens and react 24h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee sodium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for to Pb
2+absorption.Take the above-mentioned resin of 1g, add the Pb of 800mg/L
2+solution 100mL, in 30 ℃ of constant temperature water bath vibration 40min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb
2+clearance in Table 1.
Embodiment 9
Take sodium lignosulfonate 50g, be made into mass concentration and be 5% the aqueous solution, 30g furfural joins respectively in withstand voltage polyester bottles, add 5gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 15g, stir until solution mixes, airtight, be placed in 70 ° of C baking ovens and react 36h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee sodium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for to Pb
2+absorption.Take the above-mentioned resin of 1g, add the Pb of 1800mg/L
2+solution 100mL, in 30 ℃ of constant temperature water bath vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb
2+clearance in Table 1.
Embodiment 10(dynamic adsorption)
The resin of embodiment 7 preparations is used for to Pb
2+absorption.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 10, under 30 ℃, pump function, by the Pb of the 1800mg/L of 100mL
2+solution is introduced packed column, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.Pb
2+clearance in Table 1.
Embodiment 11(dynamic adsorption)
The resin of embodiment 7 preparations is used for to Pb
2+absorption.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 5, under 30 ℃, pump function, by the Pb of the 1800mg/L of 100mL
2+solution is introduced packed column, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.Pb
2+clearance in Table 1.
Embodiment 12
Take calcium lignin sulphonate 50g, be made into mass concentration and be 5% the aqueous solution, 15g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 5gSBA-15 as template, mix, stir, in reaction vessel, add sodium hydroxide 15g, stir until solution mixes, airtight, be placed in 70 ° of C baking ovens and react 36h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee calcium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.Absorption by the resin of above-mentioned preparation for Cr3+.Take the above-mentioned resin of 1g, add the Cr of 100mg/L
3+solution 100mL, in 30 ℃ of constant temperature water bath vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr
3+clearance in Table 1.
Embodiment 13
Take sodium lignosulfonate 50g, be made into mass concentration and be 30% the aqueous solution, 15g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 30g silicon sol as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 20g, stir until solution mixes, airtight, be placed in 100 ° of C baking ovens and react 24h.Then the black material of preparation is dried at 110 ° of C, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, completely exchanged to guarantee sodium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for to Cr
3+absorption.Take the above-mentioned resin of 1g, add the Cr of 100mg/L
3+solution 100mL, in 50 ℃ of constant temperature water bath vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr
3+clearance in Table 1.
Embodiment 14
The resin of embodiment 8 preparations is used for to Cr
3+absorption.Take the above-mentioned resin of 1g, add the Cr of 100mg/L
3+solution 100mL, in 50 ℃ of constant temperature water bath vibration 45min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr
3+clearance in Table 1.
Embodiment 15
The resin of embodiment 12 preparations is used for to Cd
2+absorption.Take the above-mentioned resin of 1g, add the Cd of 300mg/L
2+solution 100mL, in 30 ℃ of constant temperature water bath vibration 40min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cd
2+clearance in Table 1.
Embodiment 16(dynamic adsorption)
The resin of embodiment 12 preparations is used for to Cd
2+absorption.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 15, under 30 ℃, pump function, by the Cd of the 300mg/L of 100mL
2+solution is introduced packed column, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.Cd
2+clearance in Table 1.
Embodiment 17(dynamic adsorption)
The resin of embodiment 9 preparations is used for to Cu
2+absorption.Above-mentioned resin is filled into internal diameter 1cm, and the pillar that post length-to-diameter ratio is 15, under 30 ℃, pump function, by the Cu of the 1000mg/L of 100mL
2+solution is introduced packed column, collects effluent liquid, until solution stream after pillar, the concentration of spectrophotometric determination effluent liquid.Cu
2+clearance in Table 1.
Embodiment 18
The resin of embodiment 13 preparations is used for to Zn
2+absorption.Take the above-mentioned resin of 1g, add the Zn of 1500mg/L
2+solution 100mL, in 25 ℃ of constant temperature water bath vibration 80min, centrifugation, the concentration of spectrophotometric determination clear liquid.Zn
2+clearance in Table 1.
The clearance of multiporous biological matter resin to ion under table 1 different condition
Above-described embodiment shows, this multiporous biological matter resin is by physical adsorption and the chemisorption acting in conjunction of the kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyl, by static equilibrium, adsorb and dynamic adsorption all can be realized the fractionation by adsorption to multiple dyestuff and heavy metal ion, clearance can reach more than 90%.There is preparation technology simple, with low cost and feature that adsorption range is wide.
Claims (10)
1. the application of multiporous biological matter resin in fractionation by adsorption, is characterized in that:
Multiporous biological matter resin is contacted with dye solution or heavy metal ion solution, make dyestuff or heavy metal ion adsorbed on multiporous biological matter resin;
Being prepared as follows of described multiporous biological matter resin:
Certain density lignosulfonic acid salt brine solution, aldehyde compound, template and catalyzer are joined in reaction vessel with certain proportion, mix, at the temperature of 50 ° of C～220 ° C, after reaction 2h～120h, dry, grind, under hydrofluoric acid room temperature, process 12h and remove above template, after 0.1-2M sulfuric acid acid treatment 0.5-4h, washing, to neutral, makes this material after oven dry;
The mass concentration of described lignosulfonic acid salt brine solution is 1%～80%;
The mass ratio of described aldehyde compound and sulfonated lignin is 0.1～100:100;
Described catalyzer is an acidic catalyst or basic catalyst; In system, an acidic catalyst consumption is 0.05M～20M, and basic catalyst and sulfonated lignin mass ratio are 0.5～80:100;
The consumption of described template is 0.01～100(wt) sulfonated lignin of %.
2. the application in fractionation by adsorption according to biomass resin claimed in claim 1, is characterized in that:
Described fractionation by adsorption mode is static equilibrium absorption or dynamic adsorption;
Described static equilibrium adsorption process is to get the dye solution of certain volume concentration or heavy metal ion solution in Erlenmeyer flask, adds a certain amount of resin material, and vibration absorption for some time under certain temperature, centrifugation, measures the concentration of clear liquid; The quality consumption of described resin is 0.1～200gg
-1heavy metal ion in dyestuff or heavy metal ion solution in dye solution, described adsorption temp is 5 ° of C～60 ° C, adsorption time is 5min～300min;
Described dynamic adsorption process is for being packed into this resin material on the pillar of fractionation by adsorption, the packed column of at a certain temperature, the dye solution of certain volume concentration or heavy metal ion solution being flowed through under gravity or pressure-acting, collect the clear liquid of water outlet, measure its concentration; Described adsorption temp is 5 ° of C～60 ° C; The post length-to-diameter ratio of described fractionation by adsorption post is more than or equal to 1, and preferably post length-to-diameter ratio is 2 ~ 50, and best post length-to-diameter ratio is 5 ~ 25.
3. according to application claimed in claim 2, it is characterized in that:
Described dyestuff is basic dyestuff, dispersed dye, matching stain, reactive dyestuffs, or one or two or more kinds in substantive dyestuff; Its starting point concentration is 5mgL
-1～3000mgL
-1;
Heavy metal ion in described heavy metal ion solution is Pb
2+, Cd
2+, Cu
2+, Zn
2+, Cr
3+, Hg
2+, Fe
3+in one or two or more kinds, its starting point concentration is 5mgL
-1～2000mgL
-1;
Described volume is 100mL/g resin.
4. according to application claimed in claim 3, it is characterized in that:
The mass concentration 5-50% of hydrofluoric acid; This multiporous biological matter resin absorption to dye well metal ion, clearance can reach more than 90%.
5. according to application claimed in claim 1, it is characterized in that:
Described sulfonated lignin are one or two or more kinds in sodium lignosulfonate, magnesium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate; Preferably the mass concentration of lignosulfonic acid salt brine solution is 10%～50%;
Described aldehyde compound is alkanoic or aromatic aldehyde and derivative thereof; Preferably the mass ratio of aldehyde compound and sulfonated lignin is 1～50:100;
Described temperature of reaction is 50 ° of C～220 ° C, and the reaction times is 2h～120h.
6. according to the method described in claim 1 or 5, it is characterized in that:
The mass concentration of best lignosulfonic acid salt brine solution is 15%～35%;
Preferably aldehyde compound is one or two or more kinds in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, octanal, chloro acetaldehyde, paraformaldehyde, furfural, glutaraldehyde; Best aldehyde compound and the mass ratio of sulfonated lignin are 10～30:100;
Preferably temperature of reaction is 50 ° of C～170 ° C, and the reaction times is 2h～72h.
7. it is characterized in that in accordance with the method for claim 6:
Best aldehyde compound is formaldehyde, acetaldehyde, one or two or more kinds in paraformaldehyde and furfural;
Best temperature of reaction is 70 ° of C～150 ° C, and the reaction times is 4h～36h.
8. it is characterized in that in accordance with the method for claim 1: described template is silicon oxide, charcoal, molecular sieve SBA-3, SBA-15, SBA-16, ZSM-5, ZSM-11, ZSM-12, MCM-41, MCM-48, KIT-6, SAPO-11, SAPO-34, FDU-12, CMK-3, CMK-8, nanometer CaCO
3, one or two or more kinds in nano-MgO, silica gel; The preferable amount of described template is 0.05～30(wt) sulfonated lignin of %;
An acidic catalyst is one or two or more kinds in hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, monochloroacetic acid, Phenylsulfonic acid, tosic acid, mahogany acid, and basic catalyst is one or two or more kinds in anthraquinone, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, hydrated barta, ammonium hydroxide, calcium oxide, magnesium oxide, sodium sulphite, S-WAT, sodium carbonate, ethamine, tertiary amine, aniline, tetra-alkyl ammonium hydroxide;
Preferably an acidic catalyst consumption is 0.5M～10M(system concentration), basic catalyst and sulfonated lignin mass ratio are 1～50:100.
9. according to the method described in claim 1 or 8, it is characterized in that:
Best template is one or two or more kinds in SBA-15, ZSM-5 or silica gel; Preferably catalyzer is hydrochloric acid, oxalic acid, sodium hydroxide, ammonium hydroxide, magnesium oxide, sodium carbonate, a kind of in aniline.
10. it is characterized in that in accordance with the method for claim 9:
Best catalyzer is hydrochloric acid, oxalic acid, sodium hydroxide, a kind of in ammonium hydroxide; Best an acidic catalyst consumption is 1M～4M(system concentration), the consumption of basic catalyst and sodium lignosulfonate mass ratio are 1～30:100.
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| CN106365917A (en) * | 2016-09-19 | 2017-02-01 | 南开大学 | Slow release fertilizer production technology and using method of slow release fertilizer |
| CN106390946A (en) * | 2016-12-07 | 2017-02-15 | 郑州源冉生物技术有限公司 | Heavy metal adsorbing material with peanut shells and preparing method thereof |
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| CN104891596A (en) * | 2014-03-06 | 2015-09-09 | 上海市南洋模范中学 | Static device for rapid purification of low-concentration lead-containing wastewater by utilizing biomass material |
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| CN104923163B (en) * | 2014-03-20 | 2017-03-29 | 长沙文晟生物科技有限责任公司 | A kind of silica gel absorber of Adsorption of Heavy Metal Ions and preparation method thereof |
| CN105060584A (en) * | 2015-07-18 | 2015-11-18 | 常州市鼎日环保科技有限公司 | Method for removing heavy metals in plated plate etching wastewater |
| CN106365917A (en) * | 2016-09-19 | 2017-02-01 | 南开大学 | Slow release fertilizer production technology and using method of slow release fertilizer |
| CN106390946A (en) * | 2016-12-07 | 2017-02-15 | 郑州源冉生物技术有限公司 | Heavy metal adsorbing material with peanut shells and preparing method thereof |
| CN106390945A (en) * | 2016-12-07 | 2017-02-15 | 郑州源冉生物技术有限公司 | Heavy metal adsorbing material prepared from straws and preparation method thereof |
| CN112371093A (en) * | 2020-10-28 | 2021-02-19 | 江门市长优实业有限公司 | Nickel recovery agent and application thereof |
| CN113368829A (en) * | 2021-04-28 | 2021-09-10 | 湖北科技学院 | Spherical bio-based adsorption resin and preparation method and application thereof |
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