CN103509194A - Porous biomass acidic solid material, and preparation and application thereof - Google Patents
Porous biomass acidic solid material, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a porous biomass acidic solid material. The preparation method is characterized by comprising the following steps: adding a lignosulfonate water solution having a certain concentration, an aldehyde compound, a template agent and a catalyst into a reaction vessel according to a certain ratio, uniformly mixing, and reacting at 50-220 DEG C for 2-120 hours; drying, grinding, removing the template, performing acid treatment, and washing to neutral; and drying to obtain the material. The porous material structurally contains multiple surface acidic groups such as sulfonic groups, carboxyl groups and hydroxyl groups, has a high surface distribution density and is a favorable porous acidic solid material. The material is used for esterification reaction, and the esterification yield is up to 85% or above. The material provided by the invention has the advantages of abundant raw material sources, controllable structure, simple preparation process and the like.
Description
Technical field
The invention belongs to technical field of material, be specifically related to preparation method and the application thereof of the acid solid material of a kind of multiporous biological matter.
Background technology
Sulfonic group solid material receives publicity as a kind of acid material of alternative liquid mineral acid.The synthesis mode of this class material adopts the sulfonic method of load more, main by the compound of sulfonation is carried out to incomplete carbonization, or after organism is carried out to incomplete carbonization, these two kinds of approach of sulfonation are synthetic again.
CN10139668A is by xylogen in 50 ° of C～95 ° C sulfonation a few hours in the vitriol oil, then carbonization under ° C nitrogen protection of 300 ° of C～450, has prepared lignosulphonate solid catalyst.It is substrate that CN102218342A be take biomass and aromatic compound, at 150 ° of C～220 ° C, reacts 16～72h in still, through grinding, washing, concentrated acid sulfonation, processes, and makes sulfonation carbon solid acid catalyst.Document (J.Am.Chem.Soc.2008,130,12787-12793) take Microcrystalline Cellulose as raw material; at 450 ° of C; under nitrogen protection, carbonization makes black solid, by the sulfonation in oleum under nitrogen atmosphere of this black solid, has prepared and has contained sulfonic solid catalyst.Document (Acta Phys.-Chim.Sin., 2010,26(7): 1873-1878) adopt Mierocrystalline cellulose and Fe (NO
3)
39H
2o is raw material, under ammoniacal liquor condition, has prepared matrix material.Dried, at 400 ° of C, N
2carbonization 15h under atmosphere, obtains black solid powder.The sulfonation in oleum of this solid is processed, and then 150 ° of C hydrothermal treatment consists, have made sulfonated carbon-based solid catalyzer.Document (Green Chem., 2008,10,1033-1037) adopting gac is raw material, under argon gas atmosphere, in 150 ° of C sulfonation, processes 16h, and hot wash obtains brown powder, and then 200 ° of C hydrothermal treatment consists, make activated carbon solid catalyst.Document (Green Chem., 2011,13,2678-2681) take glucose as carbon source, tosic acid is sulphonating agent, and 180 ° of C aging 24h in still make black solid, then 180 ° of C process and remove the small organic molecule that is adsorbed on solid surface, have made sulfonation active carbon material.Document (Chem.Commun., 2010,46,6935-6937) take sucrose as raw material, SBA-15 is hard template, dip treating obtains solid.This solid, at 900 ° of C, after roasting 6h, is removed to template with hydrogen fluoride in nitrogen atmosphere, prepared CMK-3 material.This material is processed in 250 ° of C sulfonation in the vitriol oil, obtained the CMK-3 catalyzer of sulfonation.CN101485997B be take the carbohydrates such as glucose as raw material, by solvent thermal reaction, at 150 ° of C～200 ° C, carries out sulfonation and process 16～72h in reactor, and washing, dries and make carbonaceous solid acid catalyst.Adopt carbonization sulfonation mode to prepare the reaction of sulfonic group solid material, all need to be in carbonization under comparatively high temps, and need under inert atmosphere protection, carry out, cause energy consumption high, complicated process of preparation, cost is expensive.On the other hand, adopt concentrated acid sulfonation, have the shortcomings such as etching apparatus, contaminate environment.
Acid system paper-making pulping process can produce a large amount of sulfonated lignin, a kind of abundant sulfonic biomass material that contains is provided, and has contained a large amount of hydroxyls and carboxyl, can be used as synthetic acidic solid material raw material.
Document (New Chemical Materials, 2009,39, (7): 68-72) adopting sodium lignosulfonate is raw material, adopt inverse suspension polymerization technology, have prepared lignin-base resin.Document (ion-exchange and absorption, 2006,22(3): 231-236) under acidic conditions, take calcium lignosulfonate as raw material, formaldehyde is linking agent, and whiteruss is solvent phase, by inverse suspension polymerization, has prepared the controlled Spherical Lignin group ion exchange resin of particle diameter.CN1817443A is dissolved in sulfonated lignin in solvent, adds certain disperse phase, under catalyst action, reacts with aldehydes, through steps such as temperature programming, insulation, intensification distillation, separation, has prepared Lignin-Based Adsorption Material.Document (Cellulose Science and technology, 2003,11(2): 8-13) utilize inverse suspension polymerization technology, take magnesium lignosulfonate as raw material, technical oils and chlorobenzene etc. is solvent, prepared globular lignin pearl body with formaldehyde polyreaction under catalyst action.
Adopt inverse suspension polymerization technology to prepare the reaction of lignin-base material, although avoided the techniques such as high temperature and the vitriol oil, need to add certain dispersion agent, tensio-active agent, product is introduced too much impurity.After product separation, also need the organic phases such as dispersion agent, tensio-active agent to recycle complex process.In addition, the material specific surface area that adopts the method to prepare is lower, and range of application is limited.
It is raw material that the present invention adopts the by product sulfonated lignin of paper-making pulping process, develops a kind of technique simple, and reaction controllability is high, and energy consumption is low, the eco-friendly novel method of preparing porous acid solid material.
Summary of the invention
The object of the present invention is to provide the preparation method of the acid solid material of a kind of multiporous biological matter.Acid solid material prepared by the method contains sulfonic group, carboxyl and hydroxyl kinds of surface acidic-group, has vesicular structure and hole dimension is controlled, and is applied to esterification.
For achieving the above object, the present invention is by the following technical solutions:
Certain density lignosulfonic acid salt brine solution and aldehyde compound are joined in reaction vessel with certain proportion, add template, add again a certain amount of catalyzer, mix, under 50 ° of C～220 ° C, react 2h～120h, dry, grind, under hydrofluoric acid room temperature, process 12h and remove above template, 1M sulfuric acid acid treatment 2h, washing, to neutral, is dried.
Described sulfonated lignin are one or two or more kinds in sodium lignosulfonate, magnesium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate, and its mass concentration is 1%～80%; Described aldehydes is alkanoic or aromatic aldehyde and derivative thereof, and the mass ratio of described aldehydes or derivatives thereof and sulfonated lignin is 0.1～100:100; 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, nano-MgO, silica gel one or two or more kinds, the consumption of described template is 0.01～50(wt) sulfonated lignin of %; Described catalyzer is acid or alkali, and described an acidic catalyst consumption is 0.05M～20M(system concentration), basic catalyst and sodium lignosulfonate mass ratio are 0.5～80:100; Described temperature of reaction is 50 ° of C～220 ° C, and the reaction times is 2h～120h.
Be preferably: described sulfonated lignin are a kind of more than two kinds in sodium lignosulfonate, magnesium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate, and its mass concentration is 10%～50%, described aldehydes is one or two or more kinds in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, octanal, chloro acetaldehyde, paraformaldehyde, furfural, glutaraldehyde, and the mass ratio of aldehydes or derivatives thereof and sulfonated lignin is 1～50:100, described template is one or two or more kinds in SBA-15, ZSM-5 or silica gel, described an acidic catalyst is hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid, monochloroacetic acid, Phenylsulfonic acid, tosic acid, one or two or more kinds in mahogany acid, basic catalyst is 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, one or two or more kinds in tetra-alkyl ammonium hydroxide, described an acidic catalyst consumption is 0.5M～10M(system concentration), basic catalyst and sodium lignosulfonate mass ratio are 1～50:100, described temperature of reaction is 50 ° of C～170 ° C, and the reaction times is 2h～72h.
The best is: described sulfonated lignin are one or two or more kinds in sodium lignosulfonate, magnesium lignosulfonate, calcium lignin sulphonate, ammonium lignosulphonate, and its mass concentration is 15%～35%; Described aldehydes is one or two or more kinds in formaldehyde, acetaldehyde, paraformaldehyde and furfural, and the mass ratio of described aldehydes or derivatives thereof and sulfonated lignin is 10～30:100; Described template is one or two or more kinds in SBA-15, ZSM-5 or silica gel, and the preferable amount of described template is 0.05～30(wt) sulfonated lignin of %; Described catalyzer is a kind of in hydrochloric acid, oxalic acid, sodium hydroxide, ammonium hydroxide; Described an acidic catalyst consumption is 1M～4M(system concentration), the consumption of basic catalyst and sodium lignosulfonate mass ratio are 1～30:100; Described temperature of reaction is 70 ° of C～150 ° C, and the reaction times is 4h～36h.
With sulfonated lignin and aldehydes (take formaldehyde as example) as path that raw material is prepared solid material suc as formula 1.
Under acidic conditions, electrophilic substitution:
Under alkaline condition, addition reaction:
The response path of formula 1 sulfonated lignin and aldehydes (take formaldehyde as example)
Lignosulfonic acid salt concn is to affect the synthetic principal element of this material.When lignosulfonic acid salt concn is lower, polyreaction is incomplete, and concentration is high, and sulfonated lignin can not dissolve completely, causes the whole inorganic bulk of coordinating, and reaction cannot be carried out.The concentration of preferred lignosulfonic acid salt brine solution is 15%～35%.
Catalyst levels is considered based on following reason.The synthetic of resin carries out in two steps, and the first step is the addition reaction of aldehyde, generates hydroxymethyl phenol, and second step is the condensation reaction between hydroxymethyl phenol.When acidity is lower, polymerization time is long; When acidity is higher, react too violent, polymerization irregularity.When an acidic catalyst consumption appropriateness, polymerization velocity is moderate, has guaranteed that the speed of polycondensation, higher than addition reaction speed, is more conducive to form the resin that molecular weight is higher.Preferred an acidic catalyst consumption is 1M～4M(system concentration).
Template is to affect the important factor that this material duct forms.While not adding template, because the material of preparation has some performances of resin, itself has pore structure material, but size is less.The size that adds template by adjusting, can realize the regulation and control to solid material aperture.Preferred template is SBA-15, ZSM-5 or silica gel.
Suitable temperature of reaction and reaction times also can have influence on the preparation of resin.Temperature is low, and polymerization time is long, causes the wasting of resources.Temperature is high, and heat of polymerization can not be derived in time, reacts too violent, and preparation technology is difficult to control; Also can make polymerization time too short, polymerization is incomplete, and the resin of formation is unstable; Suitable temperature of reaction and reaction times just can form the material of excellent property.Preferred temperature of reaction is 70 ° of C～150 ° C, and the reaction times is 4h～36h.
Technical superiority of the present invention is:
1. raw material sources are abundant, cost is low, environmental protection, and preparation technology is simple, reaction conditions is gentle, and energy consumption is low, and processing safety is high.
2. the solid material that prepared by the method contains sulfonic group, carboxyl and hydroxyl kinds of surface acidic-group, there is very strong acidity, can be used as a kind of acid material for esterification, transesterification, carbohydrate hydrolysis reaction, alkylated reaction, catalyst preparation, biofuel such as prepares at the catalyzer of multiple reaction.
3. it is controlled that the solid material that prepared by the method has porous ，Qie aperture, can be by adding the template of different size to realize the regulation and control to resin aperture.
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 100g, be made into mass concentration and be 30% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 2
Take sodium lignosulfonate 100g, be made into mass concentration and be 30% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 3
Take sodium lignosulfonate 100g, be made into mass concentration and be 30% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add the silicon sol of 100g30%wt different-grain diameter as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 4
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add the silicon sol of 100g30%wt different-grain diameter as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 5
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 125g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 6
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 125g furfural joins respectively in withstand voltage polyester bottles, add 10g SBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 60g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 7
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 60g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 8
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 60g, stir until solution mixes, airtight, be placed in 110 ° of C baking ovens and react 36h.Then the black material of preparation is dried at 110 ° of C, grind, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 9
Take sodium lignosulfonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 60g, stir until solution mixes, airtight, be placed in 110 ° of C baking ovens and react 108h.Then the black material of preparation is dried at 110 ° of C, grind, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 10
Take calcium lignin sulphonate 100g, be made into mass concentration and be 5% the aqueous solution, 125g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 11
Take calcium lignin sulphonate 100g, be made into mass concentration and be 15% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 12
Take calcium lignin sulphonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g furfural joins respectively in withstand voltage polyester bottles, add 10gSBA-15 as template, mix, stir, to dripping massfraction in reaction vessel, be 37% hydrochloric acid 35g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 13
Take calcium lignin sulphonate 100g, be made into mass concentration and be 5% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in withstand voltage polyester bottles, add the silicon sol of 100g30%wt different-grain diameter as template, mix, stir, in reaction vessel, add sodium hydroxide 30g, 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, dry, 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 acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Comparative example 1
Take magnesium lignosulfonate 100g, be made into mass concentration and be 30% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in there-necked flask, adds sodium hydroxide 30g, 70 ° of C back flow reaction 4h.Then the black material of preparation is dried at 110 ° of C, grind, 1M vitriolization 2h, completely exchanged to guarantee magnesium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Comparative example 2
Take sodium lignosulfonate 100g, be made into mass concentration and be 30% the aqueous solution, 75g massfraction is that 37% formaldehyde solution joins respectively in there-necked flask, the hydrochloric acid 50g that to drip massfraction be 37%, 70 ° of C back flow reaction 4h.Then the black material of preparation is dried at 110 ° of C, grind, 1M vitriolization 2h, completely exchanged to guarantee magnesium ion, wash to sulfate radical-free ion, dry, obtain multiporous biological matter acid material.Neutralization titration, obtains the acid amount of this material in Table 1.Accurately weigh 0.1g sample Fruit storage 1h under 120 ° of C, be N
2under physical adsorption, obtain adsorption-desorption curve.Material is done to N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of material and aperture size are in Table 2.
Embodiment 15 material property evaluations
Catalyzer using the biomass acid material in embodiment 3 as esterification.By 5moL acetic acid, 10moL Pentyl alcohol and 15g catalyzer add in reaction flask, stir, at 130 ° of C temperature, heat, and reflux water-dividing, reaction 3h, esterification yield reaches 91%.
Embodiment 16 material property evaluations
Catalyzer using the biomass acid material in embodiment 12 as esterification.5moL acetic acid and 15moL propyl carbinol and 15g catalyzer are added in reaction flask, stir, at 120 ° of C temperature, heat, reflux water-dividing, reaction 3h, esterification yield reaches 87%.
The acid amount of the acid material that table 1 is prepared for different methods.Adopt neutralization titration, take phenolphthalein as indicator, take respectively sodium-chlor, sodium bicarbonate and sodium hydroxide and go out the amount of sulfonic group, carboxyl and hydroxyl as exchanger titration.
Specific surface area and the aperture size of the acid material that table 2 is prepared for different methods.Accurately weigh 0.1g sample Fruit storage 24h under 100 ° of C, be N
2under physical adsorption, obtain adsorption-desorption curve.The specific surface area of sample is tried to achieve by BET method, and the pore size distribution of sample is calculated by BJH method.
The acid amount of acid material prepared by table 1 different methods
The specific surface area of acid material prepared by table 2 different methods and pore size
Above-described embodiment shows, the method and do not add solid material prepared by template and contain sulfonic group, carboxyl and hydroxyl kinds of surface acidic-group has flourishing pore structure.The present invention can obtain according to the size of the template that adds the material that aperture size is different, compares with not adding material prepared by template, has compare great aperture.By this material, for esterification, esterification yield reaches more than 85%.
Claims (10)
1. the acid solid material of multiporous biological matter, is characterized in that:
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 h, 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. a preparation method for the acid solid material of multiporous biological matter described in claim 1, is characterized in that:
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, 0.1-2M sulfuric acid acid treatment 0.5-4h h, rear 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 0.01～50(wt) sulfonated lignin of %.
3. it is characterized in that in accordance with the method for claim 2:
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.
4. it is characterized in that in accordance with the method for claim 3:
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.
5. it is characterized in that in accordance with the method for claim 4:
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.
6. in accordance with the method for claim 2, 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.
7. it is characterized in that in accordance with the method for claim 2:
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;
The mass concentration 5-50% of hydrofluoric acid.
8. it is characterized in that in accordance with the method for claim 2:
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.
9. an application for the acid solid material of multiporous biological matter described in claim 1, is characterized in that:
The acid solid material of multiporous biological matter, contains sulfonic group, carboxyl and hydroxyl kinds of surface acidic-group and surface arrangement density high in its structure, be the good acid solid material of porous; By this material, for esterification, esterification yield reaches more than 85%;
An acidic catalyst making is added to the mixed system of organic acid and Organic Alcohol, reaction generates corresponding ester;
Described organic acid is one or two or more kinds in formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, pimelic acid, phenylformic acid, P-hydroxybenzoic acid, ortho-toluic acid, meta-toluic acid, terephthalic acid, stearic acid; Described Organic Alcohol is one or two or more kinds in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, phenylcarbinol, ethylene glycol, glycerol.
10. according to application claimed in claim 9, it is characterized in that: described alcohol (OH) is 1～50 with the mol ratio of acid (COOH), catalyst levels is 50mg～300g/mol(-COOH), temperature of reaction is 50 ° of C～200 ° C, reaction times is 2h～40h, stirring reaction, catalyzer centrifugation, recycling, esterification yield reaches more than 85%.
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