CN104437632A - Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof - Google Patents
Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a macro-porous acid-base dual functional organic solid catalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: adding p-styrene sulfonic acid (SS), a water-soluble polymerizable alkaline monomer, an initiating agent, a crosslinking agent and an emulsifying agent into deionized water to serve as a water phase, and stirring to ensure that the materials are mixed uniformly; dropwise adding paraffin serving as an oil phase into the water phase while continuously stirring to prepare a stable high-inner-phase emulsion; heating to 60-85 DEG C, performing polymerization reaction for 15-26 hours, performing soxhlet extraction on reactants by using acetone, and performing vacuum drying to obtain a polymer; and adding the polymer into a diluted acid solution, stirring, then filtering, washing with deionized water, and performing vacuum drying to obtain the macro-porous acid-base dual functional organic solid catalyst. The preparation method provided by the invention adopts high-inner-phase emulsion polymerization, so that the preparation process is simple and easy to operate; the prepared macro-porous solid acid-base catalyst is large in aperture, is hollow and crosslinking inside, and has both acid and alkali catalytic activity sites; and when the catalyst is applied to a test for converting cellulose into 5-hydroxymethyl furfural, the conversion rate of the catalyst is greatly improved.
Description
Technical field
The invention belongs to technical field of environment function material preparation, especially relate to the difunctional organic solid catalyst of a kind of macropore soda acid and preparation method and application.
Background technology
5 hydroxymethyl furfural (5-HMF) is a kind of important fine chemical material, can be prepared into macromolecular material, medical product etc. further by reactions such as oxidation, hydrogenation and condensations.A kind of macromolecular polysaccharide that cellulose is the widest as occurring in nature distribution, content is maximum produces one of the most Research Significance of 5-HMF and the biomass energy of development potentiality.Cellulose conversion is that 5-HMF relates to three main reactions: (1) cellobiose is converted into glucose; (2) glucose isomerase turns to fructose; (3) fructose is degraded to 5-HMF.
Be prepared as in the reaction of 5-HMF at cellulose, the homogeneous catalysts such as industrial usual use example hydrochloric acid and organic acid carry out catalytic degradation cellulose, but it the exists deficiency such as corrosive equipment, accessory substance are many, not easily separated, contaminated environment.In recent years, the solid acid catalysts such as heteropoly acid, ion exchange resin, solid super-strong acid are also applied in this reaction by people gradually.There are some researches show, the existence in catalyst neutral and alkali site will be conducive to glucose isomerase and turn to fructose.
Traditional difunction catalyst mainly contains three classes, the first kind is the inorganic material (as aluminum phosphate, hydrotalcite, mixed-metal oxides etc.) that material surface itself has acidic site and basic sites concurrently, Equations of The Second Kind is the organic material (as amino acid etc.) that material itself has acidic site and basic sites concurrently, and the 3rd class is then by introducing acidic site (as the group such as sulfonic acid, phosphoric acid) and basic sites (as amine etc.) on mesoporous material (as SBA-15, MCM-41 etc.) surface.Wherein, mesoporous material is because of advantages such as surface area are large, microcellular structure is flourishing, and Chang Zuowei modified support, is widely used.But, when there is the large reagent of viscosity in course of reaction, a large amount of blockage of the micro orifice can be caused, reducing reaction speed.
High Internal Phase Emulsion (High Internal Phase Emulsions, HIPEs) be that a kind of dispersed phase volume fraction is greater than 74.05% and reaches as high as the emulsion system of 99%, be divided into oil-in-water type (O/W) and water-in-oil type (W/O) High Internal Phase Emulsion.Have that aperture is large by the material that High Internal Phase Emulsion legal system is standby, hollow and the advantages such as crosslinked, high-permeability, low-density, be widely used in the industries such as food, pharmaceutical carrier, cosmetics, adsorbing separation and each polyporous materials of production.
Summary of the invention
Not high for acid catalyzed conversion rate in the cellulose degradation reaction existed in prior art, easily block duct when taking mesoporous material as modified support, reduce the deficiencies such as reaction rate, the invention provides the method that the difunctional organic solid catalyst of macropore soda acid is prepared in the polymerization of a kind of High Internal Phase Emulsion, be intended to obtain that a kind of aperture is comparatively large, hole inner hollow and crosslinked, have the solid catalyst of acid, basic sites concurrently.
The present invention realizes above-mentioned technical purpose by following technological means.
A preparation method for the difunctional organic solid catalyst of macropore soda acid, comprises following steps:
(1) p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initator, N, N-methylene-bisacrylamide and emulsifying agent are added in deionized water, as aqueous phase, stir and make it mix; Get paraffin as oil phase, dropwise add in aqueous phase under constantly stirring, be prepared into stable High Internal Phase Emulsion; The mass ratio of described deionized water, p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initator, N, N-methylene-bisacrylamide and emulsifying agent is (3.36-4.64): (1.06-1.34): (0.28-0.52): (0.034-0.046): (0.026-0.0358): (0.03-0.05); The volume ratio of described paraffin and deionized water is (30.24-41.76): (3.36-4.64);
(2) High Internal Phase Emulsion described in step (1) being warming up to 60-85 DEG C keeps 15-26h to carry out thermal-initiated polymerization reaction, and products therefrom obtains polymer after acetone surname extraction, vacuum drying;
(3) resulting polymers in step (2) is added stirring reaction in the dilute acid soln configured, after filtration, deionized water washing, namely obtain the difunctional organic solid catalyst of macropore soda acid after vacuum drying.
Preferably, water miscible polymerizable alkaline monomer described in step (1) is acrylamide or 1-vinyl imidazole, initator is potassium peroxydisulfate or ammonium persulfate, and emulsifying agent is sorbitan monooleate APEO (Tween80) or Tween-85 (Tween85).
Preferably, described in step (2), the temperature of polymerisation is 60-65 DEG C, and the time is 18-24h.
Preferably, dilute acid soln described in step (3) is the dilute sulfuric acid of 0.64-1.36mol/L, dust technology or watery hydrochloric acid, and the solid-to-liquid ratio of polymer and dilute acid soln is (0.36-0.64) g:50mL.
Preferably, described in step (2), vacuum drying temperature is 50-55 DEG C, and the time is 20-24h.
Preferably, described in step (3), vacuum drying temperature is 70-80 DEG C, and the time is 20-24h.
The difunctional organic solid catalyst of macropore soda acid prepared by preparation method of above-mentioned macropore soda acid difunctional organic solid catalyst.
The difunctional organic solid catalyst application of above-mentioned macropore soda acid is degraded to the reaction of 5 hydroxymethyl furfural in catalyse cellulose.
Beneficial effect of the present invention:
(1) gained solid catalyst of the present invention has acid, base catalysis avtive spot concurrently, when being applied in cellulose degradation reaction, its acidic site is conducive to promoting that cellulose conversion is glucose and the fructose converting process for 5-HMF, and basic site is conducive to the process that glucose isomerase turns to fructose, improve the productive rate of cellulosic conversion ratio and 5-HMF on the whole.
(2) gained solid catalyst aperture of the present invention is comparatively large, is conducive to the transmission speed improving large molecules fibrin, Reaction time shorten; Hole inner hollow and crosslinked, improve the contact area of reaction substrate and active site, reaction condition is gentle, and catalyst amount reduces; Possess higher permeability and low-density simultaneously.
(3) the present invention adopts High Internal Phase Emulsion polymerization, and preparation technology is simple, easy to operate, and suitability for industrialized is produced.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of High Internal Phase Emulsion in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of macropore solid acid alkali catalytic agent in embodiment 1.
Fig. 3 is that the XPS of macropore solid acid alkali catalytic agent in embodiment 1 can collection of illustrative plates.
Fig. 4 is the TGA curve of macropore solid acid alkali catalytic agent in embodiment 1.
Fig. 5 is the NH of macropore solid acid alkali catalytic agent in embodiment 1
3temperature programming desorption collection of illustrative plates.
Fig. 6 is the CO of macropore solid acid alkali catalytic agent in embodiment 1
2temperature programming desorption collection of illustrative plates.
Detailed description of the invention
The catalytic performance analysis test method of catalyst described in technique scheme is specially:
(1) catalytic test
The cellulose crystals of 2g ionic liquid 1-butyl-3-methyl imidazolium chlorine and 0.1g is joined in the single port flask of 25mL, system in the oil bath pan of 120 DEG C, pre-reaction 0.5h under the rotating speed of 800r/min.Then 0.04g catalyst is joined in reaction system, continue reaction 0.5h.After having reacted, in the middle of products therefrom constant volume to volumetric flask, after be diluted to 5000 times, detect by efficient liquid phase (HPLC).Testing conditions is: column temperature: 30 DEG C; Mobile phase is water and methyl alcohol, and ratio is 3:7; Flow velocity is 1mL/min; Determined wavelength is 283nm; Sample size is 22.5 μ L.
Sample standard curve is y=0.0019x+3.4903 (y represents the concentration that 5-HMF is corresponding, and x represents peak area).According to acquired results, calculate cellulosic conversion ratio (Y):
Y＝5000y(％)
After wherein y represents dilution according to calibration curve the concentration (mg/L) calculated; Y represents cellulosic conversion ratio (%).
(2) regeneration test
Catalytic test gained reactant liquor through centrifugal, be separated, be drying to obtain regeneration catalyst, it is put in above-mentioned catalytic test again, tests its catalytic effect; Carry out four regeneration tests in this approach.Measured catalysate detection method and experimental condition are with above-mentioned catalytic test.
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
(1) by 1.06g p styrene sulfonic acid, 0.28g acrylamide, 0.034g potassium peroxydisulfate, 0.026g N, N-methylene-bisacrylamide, 0.03g Tween 85 joins in 3.36ml deionized water and forms mixed solution as aqueous phase, and mechanical agitation made it mix after 20 minutes.Get 30.24mL paraffin as oil phase, under ceaselessly mechanical agitation, oil phase is dropwise joined in aqueous phase and mixes, stir 10min, be prepared into stable HIPEs.
(2) be warming up to 60 DEG C of maintenances and carry out thermal-initiated polymerization reaction in 18 hours, through acetone through surname extraction with wash-out Tween 85 and paraffin, by products therefrom dry 24h under 50 DEG C of vacuum, obtain polymer.
(3) configure the sulfuric acid solution of 0.64mol/L, get 0.36g polymer abrasive powdered after add in 50ml sulfuric acid solution, stir 20h, vacuum drying 21h at 70 DEG C, obtain the agent of macropore solid acid alkali catalytic.
The optical microscope photograph of HIPEs as can be seen from Fig. 1, the diameter of prepared HIPEs drop is widely distributed, and from several microns to 100 microns not etc., the tightly packed one-tenth of the drop in decentralized photo is interconnective spherical.
As can be seen from Fig. 2 catalyst scanning electron microscope (SEM) photograph in, this catalyst has perforate hollow structure, is connected between macropore by internal crosslinking hole, macropore average pore size D is 24.5 μm, connecting hole average pore size d is 6.2 μm, and catalyst has height permeability, the performances such as low-density.
The XPS energy collection of illustrative plates of Elements C, S, O, N, further demonstrates embodiment 1 and has successfully prepared the difunctional organic solid catalyst of macropore soda acid as can see from Figure 3.
From Fig. 4, the TGA curve of catalyst can be seen, gained catalyst weight-loss ratio is 72.12%, shows that it has good stability.
NH from Fig. 5
3cO in temperature programming desorption collection of illustrative plates and Fig. 6
2temperature programming desorption collection of illustrative plates, can find out, the catalyst prepared by embodiment 1 shows acidic character peak and basic character peak simultaneously.
Difunctional for prepared macropore soda acid organic solid catalyst is carried out catalytic test and regeneration test, and result shows: cellulosic conversion ratio is 41.2%, is improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst before; In catalyst regeneration process, cellulosic conversion ratio is followed successively by 40.9%, 40.5%, 40% and 39.2%, and regeneration effect is better.
Embodiment 2:
(1) by 1.2g p styrene sulfonic acid, 0.4g 1-vinyl imidazole, 0.04g ammonium persulfate, 0.0309g N, N-methylene-bisacrylamide, 0.04g Tween 80 joins in 4mL deionized water and forms mixed solution as aqueous phase, and mechanical agitation made it mix after 25 minutes.The paraffin getting 36mL is as oil phase, and under ceaselessly mechanical agitation, oil phase dropwise joins in aqueous phase and mixes, and stirs 15min, is prepared into stable HIPEs.
(2) be warming up to 50 DEG C of maintenances and carry out thermal-initiated polymerization reaction in 15 hours, through acetone through surname extraction eluting surface activating agent and paraffin, by products therefrom dry 22h under 52 DEG C of vacuum, obtain polymer.
(3) configure the salpeter solution of 1.2mol/L, get 0.5g polymer abrasive powdered after add in configured 50mL salpeter solution, stir 22h, vacuum drying 20h at 75 DEG C, obtain the agent of macropore solid acid alkali catalytic.
Difunctional for prepared macropore soda acid organic solid catalyst is carried out catalytic test and regeneration test, and result shows: cellulose conversion rate is 38.7%, is improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst; In catalyst regeneration process, cellulose conversion rate is followed successively by 38.7%, 38.5%, 38.1% and 37.9%, and regeneration effect is better.
Embodiment 3:
(1) by 1.34g p styrene sulfonic acid, 0.52g acrylamide, 0.046g potassium peroxydisulfate, 0.0358g N, N-methylene-bisacrylamide, 0.05g Tween 85 joins in 4.64g deionized water and forms mixed solution as aqueous phase, and mechanical agitation made it mix after 30 minutes.The paraffin getting 41.76mL is as oil phase, and under ceaselessly mechanical agitation, oil phase dropwise joins in aqueous phase and mixes, and mechanical agitation, after 20 minutes, is prepared into stable HIPEs.
(2) be warming up to 85 DEG C of maintenances and carry out thermal-initiated polymerization reaction in 26 hours, through acetone through surname extraction eluting surface activating agent and paraffin, by products therefrom dry 24h under 55 DEG C of vacuum, obtain polymer.
(3) configure the hydrochloric acid solution of 1.36mol/L, get 0.64g polymer abrasive powdered after add in configured 50mL sulfuric acid solution, stir 24h, vacuum drying 22h at 80 DEG C, obtain the agent of macropore solid acid alkali catalytic.
Difunctional for prepared macropore soda acid organic solid catalyst is carried out catalytic test and regeneration test, and result shows: cellulose conversion rate is 39.9%, is improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst; In catalyst regeneration process, cellulose conversion rate is followed successively by 39.5%, 38.9%, 38.1% and 37.7%, and regeneration effect is better.
Embodiment 4:
(1) by 1.3g p styrene sulfonic acid, 0.34g acrylamide, 0.04g potassium peroxydisulfate, 0.031g N, N-methylene-bisacrylamide, 0.04g Tween 85 joins in 4g deionized water and forms mixed solution as aqueous phase, and mechanical agitation made it mix after 30 minutes.The paraffin getting 35mL is as oil phase, and under ceaselessly mechanical agitation, oil phase dropwise joins in aqueous phase and mixes, and mechanical agitation, after 20 minutes, is prepared into stable HIPEs.
(2) be warming up to 65 DEG C of maintenances and carry out thermal-initiated polymerization reaction in 24 hours, through acetone through surname extraction eluting surface activating agent and paraffin, by products therefrom dry 24h under 55 DEG C of vacuum, obtain polymer.
(3) configure the sulfuric acid solution of 1mol/L, get 0.5g polymer abrasive powdered after add in configured 50mL sulfuric acid solution, stir 24h, vacuum drying 24h at 80 DEG C, obtain the agent of macropore solid acid alkali catalytic.
Difunctional for prepared macropore soda acid organic solid catalyst is carried out catalytic test and regeneration test, and result shows: cellulose conversion rate is 42.1%, is improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst; In catalyst regeneration process, cellulose conversion rate is followed successively by 42.1%, 41.9%, 41.7% and 41.5%, and regeneration effect is better.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (8)
1. a preparation method for the difunctional organic solid catalyst of macropore soda acid, is characterized in that, comprise following steps:
(1) p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initator, N, N-methylene-bisacrylamide and emulsifying agent are added in deionized water, as aqueous phase, stir and make it mix; Get paraffin as oil phase, dropwise add in aqueous phase under constantly stirring, be prepared into stable High Internal Phase Emulsion; The mass ratio of described deionized water, p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initator, N, N-methylene-bisacrylamide and emulsifying agent is (3.36-4.64): (1.06-1.34): (0.28-0.52): (0.034-0.046): (0.026-0.0358): (0.03-0.05); The volume ratio of described paraffin and deionized water is (30.24-41.76): (3.36-4.64);
(2) High Internal Phase Emulsion described in step (1) being warming up to 60-85 DEG C keeps 15-26h to carry out thermal-initiated polymerization reaction, and products therefrom obtains polymer after acetone surname extraction, vacuum drying;
(3) resulting polymers in step (2) is added stirring reaction in the dilute acid soln configured, after filtration, deionized water washing, namely obtain the difunctional organic solid catalyst of macropore soda acid after vacuum drying.
2. the preparation method of the difunctional organic solid catalyst of macropore soda acid according to claim 1, it is characterized in that, water miscible polymerizable alkaline monomer described in step (1) is acrylamide or 1-vinyl imidazole, initator is potassium peroxydisulfate or ammonium persulfate, and emulsifying agent is sorbitan monooleate APEO (Tween80) or Tween-85 (Tween85).
3. the preparation method of the difunctional organic solid catalyst of macropore soda acid according to claim 1, is characterized in that, described in step (2), the temperature of polymerisation is 60-65 DEG C, and the time is 18-24h.
4. the preparation method of the difunctional organic solid catalyst of macropore soda acid according to claim 1, it is characterized in that, dilute acid soln described in step (3) is the dilute sulfuric acid of 0.64-1.36mol/L, dust technology or watery hydrochloric acid, and the solid-to-liquid ratio of polymer and dilute acid soln is (0.36-0.64) g:50mL.
5. the preparation method of the difunctional organic solid catalyst of macropore soda acid according to claim 1, is characterized in that, described in step (2), vacuum drying temperature is 50-55 DEG C, and the time is 20-24h.
6. the preparation method of the difunctional organic solid catalyst of macropore soda acid according to claim 1, is characterized in that, described in step (3), vacuum drying temperature is 70-80 DEG C, and the time is 20-24h.
7. the difunctional organic solid catalyst of the macropore soda acid prepared by preparation method of macropore soda acid according to claim 1 difunctional organic solid catalyst.
8. the difunctional organic solid catalyst application of macropore soda acid according to claim 7 is degraded to the reaction of 5 hydroxymethyl furfural in catalyse cellulose.
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