CN103508508B - The application in adsorbing separation of a kind of multiporous biological matter resin - Google Patents
The application in adsorbing separation of a kind of multiporous biological matter resin Download PDFInfo
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Abstract
The present invention relates to a kind of multiporous biological matter resin and the application in adsorbing separation thereof, mainly the biomass resin containing kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyls is used for Wastewater Dyes and metal biosorption separates.This resin is by combineds effect such as ion exchange, physical absorption, complexation and Hole bottom cavity blast, it is achieved that to multiple dyestuff and metal biosorption, clearance can reach more than 90%.
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 adsorbing separation thereof.
Background technology
Waste water from dyestuff and the harm of toxic heavy metal Wastewater on Ecological Environmental are very big.After toxic wastewater entered environment, being difficult to be biodegradable, toxic element is accumulated in vivo by food chain, destroys organism normal physiological metabolic activity, is detrimental to health.The conventional processing method of waste water has the methods such as the sedimentation method, electrolysis, reducing process, extraction, ion exchange, absorption.
Absorption method carries out water process, owing to it is applied widely, high treating effect, recyclable useful material and the advantage such as adsorbent is reusable, is widely used to the fields such as chemical industry, environmental conservation, medical and health and biological engineering.Along with constantly improving of existing performance of the adsorbent and succeeding in developing of new adsorbent, absorption method application prospect in water processes is more wide.
At present, the non-renewable resources such as oil are increasingly exhausted, and people have turned one's attention to Renewable resource.Lignin is the Main By product of wood hydrolysis industry and pulp and paper industry, if being not fully utilized, and not only serious environment pollution, will also result in the significant waste of resource.In recent years, people are by the controlled chemical modification (sulfuration, sulfomethylation, methylolation, grafting, condensation etc.) to lignin structure, improve its chemical reactivity or control its aggregated structure and interaction force intensity, strengthening its surface activity, to improve its absorption property.
Acid system paper-making pulping process can produce substantial amounts of lignosulfonates.For Appropriate application in addition, reduce and environment is threatened, with lignosulfonates for body material, the solid lignin adsorbing material of synthesizing new environmental protection in eco-friendly chemical mediator, separation for heavy metal ion, the process of waste water from dyestuff, thus reaching the purpose of the treatment of wastes with processes of wastes against one another, is conducive to efficiently separating of adsorbing material and waste water simultaneously.
It is raw material that document (New Chemical Materials, 2009,39, (7): 68-72) adopts sodium lignin sulfonate, utilizes inverse suspension polymerization technology, is prepared for lignin-base resin.And have studied its heavy metal ion Pb2+、Cd2+Absorption property.Document (ion exchange and absorption, 2006,22(3): 231-236) with calcium lignosulfonate for raw material, in acid condition, with formaldehyde for cross-linking agent, liquid paraffin is organic facies, it is prepared for the Spherical Lignin group ion exchange resin of size tunable by inverse suspension polymerization, have studied them to Cr3+Absorption property.Document (China papermaking journal, 2005,20(1) 111-113) to adopt Lignosite and formaldehyde be raw material, utilize inverse suspension polymerization technology, using liquid paraffin and a small amount of surfactant as organic facies, prepare spherical lignin base ion exchange resin, and have studied resin to Cr3+And Cr2O7 2-Characterization of adsorption.Document (Environmental science and technology, 2009,32(1) 71-74) with sodium lignin sulfonate and formaldehyde for raw material, liquid paraffin is organic facies, and surfactant is dispersant, ramped heating schedule, and sample, through pretreatment, obtains solid lignin adsorbing material.Investigate its dye of positive ion methylene blue adsorption number performance.
It is currently used for dye adsorption and separation of heavy metal ions material, major part adopts inverse suspension polymerization technology to prepare with biomass for raw material, need to add certain dispersant, surfactant, in addition it is also necessary to the strict consumption controlling stir speed (S.S.) and dispersant, to ensure the adsorption effect of resin.Also the organic facies such as dispersant, surfactant is recycled after separation, complex process.The addition of organic facies, adds again cost.
Therefore, with the circuit that simple preparation technology, environmental friendliness and cost are low, develop a kind of biomass resin with relatively high absorption property, and be capable of the purpose of the treatment of wastes with processes of wastes against one another, become the focus that research worker is paid close attention to.
Summary of the invention
A kind of method that it is an object of the invention to provide wastewater treatment, it is important that the preparation of the adsorbent multiporous biological matter resin for wastewater treatment.This resin produces substantial amounts of lignosulfonates for raw material in acid system paper-making pulping process, the organic solvent such as dispersant and surfactant need not be added, under the reaction condition that gentleness is controlled, by environmental friendliness circuit combination, there is the kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyl.Use it for the adsorbing separation of multiple dyestuff and heavy metal, it is achieved that the purpose 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 catalyst, completed by following processing step: certain density lignin sulfonic acid saline solution, aldehyde compound, template and catalyst are joined in reaction vessel with certain proportion, mix homogeneously, at the temperature of 50 ° of C～220 ° C, after reaction 2h～120h, dry, grind, processing more than 12h under Fluohydric acid. room temperature and remove template, after 1M sulphuric acid acid treatment 2h, washing is to neutral, prepares this material after drying.This resin is used for dyestuff and metal biosorption, and clearance can reach more than 90%.Clearance=(Co-Ce)/Co× 100%.；CoAnd CEThe respectively concentration of effects of ion before and after absorption.
The step that is embodied as of this resin static equilibrium absorption is:
Taking initial concentration is 5mg L-1～3000mg L-1Dye solution or initial concentration are 5mg L-1～2000mg L-1Heavy metal ion solution 100mL in conical flask, take this resin material of 1g in wherein, vibrate a period of time, centrifugation, measure the concentration of clear liquid, investigate the clearance of ion.Adsorption temp is 5 ° of C～50 ° C, and adsorption time is 5min～300min.The dyestuff being suitable for is basic stain, disperse dyes, acid stain, reactive dye, direct dyes etc.；The heavy metal ion being suitable for is Pb2+, Cd2+, Cu2+, Zn2+, Cr3+Deng.
The step that is embodied as of this resin dynamic adsorption is:
This resin material is packed into internal diameter certain, the post draw ratio pillar be more than or equal to 1, certain density dye solution or heavy metal ion solution introduce in packed column by gravity or under pressure, after flowing through this material, collect the clear liquid of outlet, measure concentration, investigate the clearance of ion.Preferably draw ratio is 2 ~ 50.Best ratio is 5 ~ 25.The dyestuff being suitable for is basic stain, disperse dyes, acid stain, reactive dye, direct dyes etc.；The heavy metal ion being suitable for is Pb2+, Cd2+, Cu2+, Zn2+, Cr3+Deng.Dye solution initial concentration is 5mg L-1～3000mg L-1, heavy metal ion initial concentration solution 5mg L-1～2000mg L-1.Adsorption temp is 5 ° of C～60 ° C.
The absorption of ion is usually chemisorbed and the coefficient result of physical absorption, and needs there is adsorption site.Adopting biomass resin prepared by said method to there is sulfonic group, carboxyl and hydroxyl kinds of surface oxy radical, these functional groups can as dyestuff and metal biosorption site.Ion is produced chelation by the bonding actions such as oxy radical passes through hydrogen bond, sat linkage, generates lignin-base resin metallic sequestration thing, shows metal biosorption.Ion exchange also has certain effect in absorption, and highly acid oxy radical can be replaced with dyestuff or metal ion.Loose structure can cause Hole bottom cavity blast, thus adsorbing dyestuff or the metal ion of corresponding size.Ion exchange, physical absorption, complexation and Hole bottom cavity blast comprehensive function so that this resin has the stronger absorbability to dyestuff and heavy metal ion.
The rate of adsorption that the impact of adsorption effect is mainly reflected in early stage by temperature is different.The absorption of ion is the endothermic reaction by resin, heats up and is conducive to chemisorbed.Temperature is more high, and early stage adsorption rate is more fast, prolongation over time, and the chemisorbed site in resin is progressively occupied by ion, and resin surface adsorbate tends to 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, waste water from dyestuff is had good adsorption effect by resin.
In the solion that initial concentration is high, the adsorbance of resin is also high, and namely adsorbance increases along with the rising of ion concentration；But when ion concentration is too high, adsorption capacity tends to saturated along with constantly raising of concentration of metal ions, and adsorption rate declines therewith.
In dynamic adsorption, suitable draw ratio is to realize the important parameter that high efficiency separates.When major diameter is relatively larger, adsorbing separation is effective, but Pressure Drop is relatively big, and flow resistance is big, and the requirement of the requirement of granule strength and the life-span of adsorbate is improved, and adsorption efficiency also reduces accordingly simultaneously；Major diameter is smaller, adsorbing separation heterodyne.
The present invention, compared with traditional adsorbing material, has following several advantage:
1. abundant raw material source of the present invention, reaction condition is gentle, it is not necessary to adding the organic solvent such as dispersant and surfactant, cost is low, and preparation technology is simple.
2. the present invention is using kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyls as adsorption site, it is possible to realize the adsorbing separation to dyestuff and heavy metal ion by combineds effect such as ion exchange, physical absorption, complexing and Hole bottom cavity blast.
3. there is universality in adsorbing separation, it is adaptable to basic stain, disperse dyes, acid stain, reactive dye, dyestuff and the Pb such as direct dyes2+, Cd2+, Cu2+, Zn2+, Cr3+Etc. the absorption of contents of many kinds of heavy metal ion, and have the advantages that clearance is high.
Accompanying drawing illustrates:
Fig. 1 is static equilibrium absorption and dynamic equilibrium adsorption schematic diagram.A static equilibrium is adsorbed, B dynamic adsorption.
Fig. 2 is in static equilibrium absorption, the relation of the clearance of Methylene Blue Ion and adsorption time and temperature.
Detailed description of the invention:
The following example will be explained in further detail the present invention, but present invention is not limited thereto.
Embodiment 1
Weigh magnesium lignosulfonate 50g, it is made into the aqueous solution that mass concentration is 30%, 35g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 5gSBA-15 as template, mixing, stirring, the hydrochloric acid 12g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 100 ° of C baking ovens and reacts 24h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that magnesium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for the absorption of methylene blue.Weigh the above-mentioned resin of 1g, add the methylene blue solution 100mL of 1000mg/L, in 30 DEG C of constant temperature water baths vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 2
Weigh sodium lignin sulfonate 50g, it is made into the aqueous solution that mass concentration is 30%, 30g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 5gSBA-15 as template, mixing, stirring, the hydrochloric acid 15g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 100 ° of C baking ovens and reacts 24h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that sodium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for the absorption of methylene blue.Weigh the above-mentioned resin of 1g, add the methylene blue solution 100mL of 2500mg/L, in 30 DEG C of constant temperature water baths vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 3
Resin prepared by embodiment 2 is used for the absorption of methylene blue.Weighing the above-mentioned resin of 1g, add the methylene blue solution 100mL of 100mg/L, in 30 DEG C of constant temperature water baths vibration 100min, centrifugation, the concentration of spectrophotometric determination clear liquid, the clearance of methylene blue is in Table 1.
Embodiment 4
Resin prepared by embodiment 2 is used for the absorption of methylene blue.Weigh the above-mentioned resin of 1g, add the methylene blue solution 100mL of 100mg/L, in 30 DEG C of constant temperature water baths vibration 30min, centrifugation, the concentration of spectrophotometric determination clear liquid.The clearance of methylene blue is in Table 1.
Embodiment 5(dynamic adsorption)
Resin prepared by embodiment 2 is used for the absorption of methylene blue.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 10,30 DEG C, under pump function, the methylene blue solution of the 2500mg/L of 100mL is introduced packed column, collect effluent, flow through after pillar until solution, the concentration of spectrophotometric determination effluent.The clearance of methylene blue is in Table 1.
Embodiment 6(dynamic adsorption)
Resin prepared by embodiment 2 is used for the absorption of methylene blue.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 20,30 DEG C, under pump function, the methylene blue solution of the 2500mg/L of 100mL is introduced packed column, collect effluent, flow through after pillar until solution, the concentration of spectrophotometric determination effluent.The clearance of methylene blue is in Table 1.
Embodiment 7
Weigh sodium lignin sulfonate 50g, it is made into the aqueous solution that mass concentration is 5%, 15g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 30g Ludox as template, mixing, stirring, the hydrochloric acid 15g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 100 ° of C baking ovens and reacts 24h.Then the black material of preparation is dried at 110 ° of C, grind, remove template, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that sodium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for Pb2+Absorption.Weigh the above-mentioned resin of 1g, add the Pb of 800mg/L2+Solution 100mL, in 25 DEG C of constant temperature water baths vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb2+Clearance in Table 1.
Embodiment 8
Weigh sodium lignin sulfonate 50g, it is made into the aqueous solution that mass concentration is 5%, 25g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 30g Ludox as template, mixing, stirring, the hydrochloric acid 12g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 100 ° of C baking ovens and reacts 24h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that sodium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for Pb2+Absorption.Weigh the above-mentioned resin of 1g, add the Pb of 800mg/L2+Solution 100mL, in 30 DEG C of constant temperature water baths vibration 40min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb2+Clearance in Table 1.
Embodiment 9
Weigh sodium lignin sulfonate 50g, it is made into the aqueous solution that mass concentration is 5%, 30g furfural is added separately in pressure polyester bottles, add 5gSBA-15 as template, mixing, stirring, the hydrochloric acid 15g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 70 ° of C baking ovens and reacts 36h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that sodium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for Pb2+Absorption.Weigh the above-mentioned resin of 1g, add the Pb of 1800mg/L2+Solution 100mL, in 30 DEG C of constant temperature water baths vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Pb2+Clearance in Table 1.
Embodiment 10(dynamic adsorption)
Resin prepared by embodiment 7 is used for Pb2+Absorption.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 10,30 DEG C, under pump function, by the Pb of the 1800mg/L of 100mL2+Solution introduces packed column, collects effluent, flows through after pillar until solution, the concentration of spectrophotometric determination effluent.Pb2+Clearance in Table 1.
Embodiment 11(dynamic adsorption)
Resin prepared by embodiment 7 is used for Pb2+Absorption.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 5,30 DEG C, under pump function, by the Pb of the 1800mg/L of 100mL2+Solution introduces packed column, collects effluent, flows through after pillar until solution, the concentration of spectrophotometric determination effluent.Pb2+Clearance in Table 1.
Embodiment 12
Weigh calcium lignosulfonate 50g, it is made into the aqueous solution that mass concentration is 5%, 15g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 5gSBA-15 as template, mixing, stirring, sodium hydroxide 15g is added in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 70 ° of C baking ovens and reacts 36h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that calcium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for the absorption of Cr3+.Weigh the above-mentioned resin of 1g, add the Cr of 100mg/L3+Solution 100mL, in 30 DEG C of constant temperature water baths vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr3+Clearance in Table 1.
Embodiment 13
Weigh sodium lignin sulfonate 50g, it is made into the aqueous solution that mass concentration is 30%, 15g mass fraction is that 37% formalin is added separately in pressure polyester bottles, add 30g Ludox as template, mixing, stirring, the hydrochloric acid 20g that mass fraction is 37% is dripped in reaction vessel, stirring is until solution mix homogeneously, airtight, is placed in 100 ° of C baking ovens and reacts 24h.Then the black material of preparation is dried at 110 ° of C, grind, process more than 12h under Fluohydric acid. room temperature and remove template, 1M sulphuric acid acid treatment 2h, to ensure that sodium ion is completely exchanged, wash to sulfate radical-free ion, dry, obtain multiporous biological matter resin.The resin of above-mentioned preparation is used for Cr3+Absorption.Weigh the above-mentioned resin of 1g, add the Cr of 100mg/L3+Solution 100mL, in 50 DEG C of constant temperature water baths vibration 120min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr3+Clearance in Table 1.
Embodiment 14
Resin prepared by embodiment 8 is used for Cr3+Absorption.Weigh the above-mentioned resin of 1g, add the Cr of 100mg/L3+Solution 100mL, in 50 DEG C of constant temperature water baths vibration 45min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cr3+Clearance in Table 1.
Embodiment 15
Resin prepared by embodiment 12 is used for Cd2+Absorption.Weigh the above-mentioned resin of 1g, add the Cd of 300mg/L2+Solution 100mL, in 30 DEG C of constant temperature water baths vibration 40min, centrifugation, the concentration of spectrophotometric determination clear liquid.Cd2+Clearance in Table 1.
Embodiment 16(dynamic adsorption)
Resin prepared by embodiment 12 is used for Cd2+Absorption.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 15,30 DEG C, under pump function, by the Cd of the 300mg/L of 100mL2+Solution introduces packed column, collects effluent, flows through after pillar until solution, the concentration of spectrophotometric determination effluent.Cd2+Clearance in Table 1.
Embodiment 17(dynamic adsorption)
Resin prepared by embodiment 9 is used for Cu2+Absorption.Above-mentioned resin fills into internal diameter 1cm, and post draw ratio is the pillar of 15,30 DEG C, under pump function, by the Cu of the 1000mg/L of 100mL2+Solution introduces packed column, collects effluent, flows through after pillar until solution, the concentration of spectrophotometric determination effluent.Cu2+Clearance in Table 1.
Embodiment 18
Resin prepared by embodiment 13 is used for Zn2+Absorption.Weigh the above-mentioned resin of 1g, add the Zn of 1500mg/L2+Solution 100mL, in 25 DEG C of constant temperature water baths vibration 80min, centrifugation, the concentration of spectrophotometric determination clear liquid.Zn2+Clearance in Table 1.
The multiporous biological matter resin clearance to ion under table 1 different condition
Above-described embodiment shows, this multiporous biological matter resin passes through physical absorption and the chemisorbed combined effect of the kinds of surface oxy radicals such as sulfonic group, carboxyl and hydroxyl, being adsorbed by static equilibrium and dynamic adsorption is all capable of the adsorbing separation to multiple dyestuff and heavy metal ion, clearance can reach more than 90%.There is preparation technology simple, the feature that with low cost and adsorption range is wide.
Claims (10)
1. the multiporous biological matter resin application in adsorbing separation, it is characterised in that:
Multiporous biological matter resin is contacted with dye solution or heavy metal ion solution, makes dyestuff or heavy metal ion adsorbed on multiporous biological matter resin；
Preparing of described multiporous biological matter resin is as follows:
Certain density lignin sulfonic acid saline solution, aldehyde compound, template and catalyst are joined in reaction vessel with certain proportion, mix homogeneously, at the temperature of 50 DEG C～220 DEG C, after reaction 2h～120h, dry, grind, process more than 12h under Fluohydric acid. room temperature and remove template, after 0.1-2M sulphuric acid acid treatment 0.5-4h, washing is to neutral, prepares this material after drying；
The mass concentration of described lignin sulfonic acid saline solution is 1%～80%；
The mass ratio of described aldehyde compound and lignosulfonates is 0.1～100:100；
Described catalyst is acidic catalyst or base catalyst；In system, acidic catalyst consumption is 0.05M～20M, and base catalyst and lignosulfonates mass ratio are 0.5～80:100；
The consumption of described template is the lignosulfonates of 0.01～100 (wt) %.
2. the application in adsorbing separation of the biomass resin described in claim 1, it is characterised in that:
Described adsorbing separation mode is dynamic adsorption；
Described dynamic adsorption process is that this resin material is packed into the pillar of adsorbing separation, at a certain temperature the dye solution of certain volume concentration or heavy metal ion solution are flowed through packed column by gravity or under pressure, collect the clear liquid of outlet, measure its concentration；Described adsorption temp is 5 DEG C～60 DEG C；The post draw ratio of described adsorbing separation post is be more than or equal to 1.
3. the application described in claim 2, it is characterised in that:
Described dyestuff is basic stain, disperse dyes, acid stain, reactive dye, or one or two or more kinds in direct dyes；Its initial concentration is 5mg L-1～3000mg L-1；
Heavy metal ion in described heavy metal ion solution is Pb2+, Cd2+, Cu2+, Zn2+, Cr3+, Hg2+, Fe3+In one or two or more kinds, its initial concentration is 5mg L-1～2000mg L-1；
Described volume is 100mL/g resin,
The post draw ratio of described adsorbing separation post is 2～50.
4. the application described in claim 3, it is characterised in that:
The mass concentration 5-50% of Fluohydric acid.；This multiporous biological matter resin is to dyestuff and metal biosorption, and clearance can reach more than 90%, and the post draw ratio of described adsorbing separation post is 5～25.
5. the application described in claim 1, it is characterised in that:
Described lignosulfonates are one or two or more kinds in sodium lignin sulfonate, magnesium lignosulfonate, calcium lignosulfonate, ammonium lignosulphonate；Preferably the mass concentration of lignin sulfonic acid saline solution is 10%～50%；
Described aldehyde compound is fatty aldehyde or aromatic aldehyde and derivant thereof；Preferably aldehyde compound is 1～50:100 with the mass ratio of lignosulfonates；
Described reaction temperature is 50 DEG C～220 DEG C, and the response time is 2h～120h.
6. the application described in claim 1 or 5, it is characterised in that:
The mass concentration of best lignin sulfonic acid saline solution is 15%～35%；
Preferably aldehyde compound is one or two or more kinds in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, octanal, chloroacetaldehyde, paraformaldehyde, furfural, glutaraldehyde；Best aldehyde compound and the mass ratio of lignosulfonates are 10～30:100；
Preferably reaction temperature is 50 DEG C～170 DEG C, and the response time is 2h～72h.
7. the application described in claim 6, it is characterised in that:
Best aldehyde compound is formaldehyde, acetaldehyde, paraformaldehyde and one or two or more kinds in furfural；
Best reaction temperature is 70 DEG C～150 DEG C, and the response time is 4h～36h.
8. the application described in claim 1, it is characterised in that: 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, Nano-meter CaCO33, nano-MgO, one or two or more kinds in silica gel；The consumption of described template is the lignosulfonates of 0.05～30% by weight percentage；
Acidic catalyst is one or two or more kinds in hydrochloric acid, phosphoric acid, sulphuric acid, oxalic acid, monochloroacetic acid, benzenesulfonic acid, p-methyl benzenesulfonic acid, mahogany acid, and base catalyst is one or two or more kinds in anthraquinone, potassium hydroxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, Lithium hydrate, barium hydroxide, ammonium hydroxide, calcium oxide, magnesium oxide, sodium sulfide, sodium sulfite, sodium carbonate, ethamine, tertiary amine, aniline, tetra-alkyl ammonium hydroxide；Acidic catalyst consumption is calculated as 0.5M～10M with system concentration, and base catalyst and lignosulfonates mass ratio are 1～50:100.
9. the application described in claim 1 or 8, it is characterised in that:
Template is one or two or more kinds in SBA-15, ZSM-5 or silica gel；Catalyst is hydrochloric acid, oxalic acid, sodium hydroxide, ammonium hydroxide, magnesium oxide, sodium carbonate, the one in aniline.
10. the application described in claim 9, it is characterised in that:
Catalyst is hydrochloric acid, oxalic acid, sodium hydroxide, the one in ammonium hydroxide；Acidic catalyst consumption is calculated as 1M～4M with system concentration, and the consumption of base catalyst and sodium lignin sulfonate mass ratio are 1～30:100.
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