CN104437632B - A kind of macropore soda acid difunctional organic solid catalyst and preparation method and application - Google Patents
A kind of macropore soda acid difunctional organic solid catalyst and preparation method and application Download PDFInfo
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- CN104437632B CN104437632B CN201410609635.1A CN201410609635A CN104437632B CN 104437632 B CN104437632 B CN 104437632B CN 201410609635 A CN201410609635 A CN 201410609635A CN 104437632 B CN104437632 B CN 104437632B
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Abstract
The invention provides a kind of macropore soda acid difunctional organic solid catalyst and preparation method and application, p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initiator, crosslinking agent and emulsifying agent are added in deionized water, as aqueous phase, stirring makes it mix；Take paraffin as oil phase, be added dropwise in aqueous phase under being stirred continuously, be prepared as stable High Internal Phase Emulsion；Be warming up to 60 85 DEG C of polymerisation 15 26h, reactant through acetone surname extraction, be vacuum dried to obtain polymer；Polymer is added in dilute acid soln, after stirring through filtering, deionized water washing, be vacuum dried and i.e. obtain macropore soda acid difunctional organic solid catalyst.The present invention uses High Internal Phase Emulsion to be polymerized, and preparation technology is simply, easily operate；Obtained macropore solid acid alkali catalytic agent aperture is big, hole inner hollow and crosslinking, has acid, base catalysis avtive spot concurrently；Being applied in the test that cellulose is converted into 5 hydroxymethylfurfurals, conversion ratio obtains bigger raising.
Description
Technical field
The invention belongs to technical field of environment function material preparation, especially relate to a kind of macropore soda acid difunctional organic solid catalysis
Agent and preparation method and application.
Background technology
5 hydroxymethyl furfural (5-HMF) is a kind of important fine chemical material, and being reacted by aoxidize, hydrogenate and condensation etc. can
It is further prepared into macromolecular material, medical product etc..Cellulose is big as being distributed one the widest, that content is most in nature
Molecular polysaccharide, is one of biomass energy producing the most Research Significance of 5-HMF and development potentiality.Cellulose is converted into
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.
In cellulose is prepared as the reaction of 5-HMF, the homogeneous catalyst such as industrial usual use example hydrochloric acid and organic acid is catalyzed
Degraded cellulose, but its there is corrosive equipment, accessory substance is many, be not readily separated, pollute the deficiencies such as environment.In recent years, people
The most gradually the solid acid catalysts such as heteropoly acid, ion exchange resin, solid super-strong acid are applied in this reaction.There is research table
Bright, the existence in catalyst neutral and alkali site is beneficial to glucose isomerase and turns to fructose.
Traditional difunction catalyst mainly has three classes, and the first kind is the nothing that material surface itself has acidic site and basic sites concurrently
Machine material (such as aluminum phosphate, hydrotalcite, mixed-metal oxides etc.), Equations of The Second Kind is that material itself has acidic site and basic sites concurrently
Organic material (such as amino acid etc.), the 3rd class is then by introducing on mesoporous material (such as SBA-15, MCM-41 etc.) surface
Acidic site (such as the group such as sulfonic acid, phosphoric acid) and basic sites (such as amine etc.).Wherein, mesoporous material is because surface area is big, microcellular structure
The advantages such as prosperity, frequently as modified support, are widely used.But, when course of reaction exists the big reagent of viscosity,
A large amount of blockage of the micro orifice can be caused, reduce reaction speed.
High Internal Phase Emulsion (High Internal Phase Emulsions, HIPEs) is that a kind of dispersed phase volume fraction is more than 74.05%
And reach as high as 99% emulsion system, be divided into oil-in-water type (O/W) and water-in-oil type (W/O) High Internal Phase Emulsion.Pass through
The advantages such as material prepared by High Internal Phase Emulsion method has that aperture is big, hollow and crosslinking, high-permeability, low-density, extensively should
For industries such as food, pharmaceutical carrier, cosmetics, adsorbing separation and each polyporous materials of production.
Summary of the invention
The highest, during with mesoporous material for modified support for acid catalyzed conversion rate in cellulose degradation reaction present in prior art
Easily blocking duct, reduce the deficiency such as reaction rate, the invention provides a kind of High Internal Phase Emulsion polymerization, to prepare macropore soda acid difunctional
A kind of method of organic solid catalyst, it is intended to obtain that aperture is relatively big, hole inner hollow and crosslinking, has acid, the consolidating of basic sites concurrently
Body catalyst.
The present invention realizes above-mentioned technical purpose by techniques below means.
The preparation method of a kind of macropore soda acid difunctional organic solid catalyst, comprises the steps of
(1) by p styrene sulfonic acid (SS), water miscible polymerizable alkaline monomer, initiator, N, N-methylene bisacrylamide acyl
Amine and emulsifying agent add in deionized water, and as aqueous phase, stirring makes it mix；Take paraffin as oil phase, be stirred continuously
Under be added dropwise in aqueous phase, be prepared as stable High Internal Phase Emulsion；Described deionized water, p styrene sulfonic acid (SS), water solubility
The mass ratio of polymerizable alkaline monomer, initiator, N,N methylene bis acrylamide and emulsifying agent be
(3.36-4.64):(1.06-1.34):(0.28-0.52):(0.034-0.046):(0.026-0.0358):(0.03-0.05)；Described paraffin and deionization
The volume ratio of water is (30.24-41.76): (3.36-4.64)；
(2) High Internal Phase Emulsion described in step (1) is warming up to 60-85 DEG C keeps 15-26h to carry out thermal-initiated polymerization reaction,
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, through filtration, deionized water
Macropore soda acid difunctional organic solid catalyst is i.e. obtained after washing, vacuum drying.
Preferably, water miscible polymerizable alkaline monomer described in step (1) is acrylamide or 1-vinyl imidazole, initiator
For potassium peroxydisulfate or ammonium persulfate, emulsifying agent is sorbitan monooleate APEO (Tween80) or polyoxyethylene mountain
Pears sugar alcohol acid anhydride trioleate (Tween85).
Preferably, described in step (2), the temperature of polymerisation is 60-65 DEG C, and the time is 18-24h.
Preferably, described in step (3), dilute acid soln is the dilute sulfuric acid of 0.64-1.36mol/L, dust technology or watery hydrochloric acid, polymerization
Thing is (0.36-0.64) g:50mL with the solid-to-liquid ratio of dilute acid soln.
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.
Macropore soda acid difunctional organic solid prepared by the preparation method catalysis of above-mentioned macropore soda acid difunctional organic solid catalyst
Agent.
Above-mentioned macropore soda acid difunctional organic solid catalyst is applied to catalysis fibre element and is degraded to the reaction of 5 hydroxymethyl furfural.
Beneficial effects 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 may advantageously facilitate cellulose and is converted into glucose and the fructose converting process for 5-HMF, and basic site is conducive to
Glucose isomerase turns to the process of fructose, improves the conversion ratio of cellulose and the productivity of 5-HMF on the whole.
(2) gained solid catalyst aperture of the present invention is relatively big, is conducive to improving the transmission speed of big molecules fibrin, shortens reaction
Time；Hole inner hollow and crosslinking, improve the contact area of reaction substrate and active site, and reaction condition is gentle, urges
Agent consumption reduces；It is provided simultaneously with higher permeability and low-density.
(3) present invention uses High Internal Phase Emulsion polymerization, preparation technology simply, easily operate, production suitable for industrialized.
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 13Temperature programming desorption collection of illustrative plates.
Fig. 6 is the CO of macropore solid acid alkali catalytic agent in embodiment 12Temperature programming desorption collection of illustrative plates.
Detailed description of the invention
The catalytic performance analysis test method of catalyst described in technique scheme particularly as follows:
(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 reaction
In 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, with height
Effect liquid phase (HPLC) detects.Testing conditions is: column temperature: 30 DEG C；Flowing is water and methyl alcohol mutually, and ratio is 3:7；Stream
Speed is 1mL/min；Detection 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 institute
Obtain result, the conversion ratio (Y) of calculating cellulose:
Y=5000y (%)
According to the calibration curve counted concentration of institute (mg/L) after wherein y represents dilution；Y represents the conversion ratio (%) of cellulose.
(2) regeneration test
It, through being centrifuged, separate, being drying to obtain regeneration catalyst, is put into above-mentioned urging by catalytic test gained reactant liquor again
Change in test, test its catalytic effect；Carry out four regeneration tests in this approach.Measured catalysate detection method and examination
Condition of testing is with above-mentioned catalytic test.
Below in conjunction with the accompanying drawings 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-di-2-ethylhexylphosphine oxide
Acrylamide, 0.03g Tween 85 joins and forms mixed solution in 3.36ml deionized water as aqueous phase, mechanical agitation 20 points
It is made to mix after clock.Take 30.24mL paraffin as oil phase, under ceaselessly mechanical agitation, oil phase is added dropwise over
Mix in aqueous phase, stir 10min, be prepared as stable HIPEs.
(2) it is warming up to 60 DEG C of holdings and within 18 hours, carries out thermal-initiated polymerization reaction, through acetone through surname extraction to elute Tween 85
And paraffin, products therefrom is dried under 50 DEG C of vacuum 24h, obtains polymer.
(3) configure the sulfuric acid solution of 0.64mol/L, take and add in 50ml sulfuric acid solution after 0.36g polymer is ground into powder,
Stirring 20h, is vacuum dried 21h at 70 DEG C, obtains macropore solid acid alkali catalytic agent.
From Fig. 1, the optical microscope photograph of HIPEs is it can be seen that the diameter of prepared HIPEs drop is widely distributed, from
Several microns to 100 microns, the tightly packed one-tenth of drop in dispersion phase is interconnective spherical.
It can be seen that this catalyst has perforate hollow structure in the scanning electron microscope (SEM) photograph of catalyst from Fig. 2, pass through between macropore
Internal crosslinking hole connects, and macropore average pore size D is 24.5 μm, and connecting hole average pore size d is 6.2 μm, and catalyst has height
Degree permeability, the performance such as low-density.
The XPS energy collection of illustrative plates of Elements C, S, O, N, further demonstrates embodiment 1 and is successfully prepared as can see from Figure 3
Macropore soda acid difunctional organic solid catalyst.
From Fig. 4, the TGA curve of catalyst is it will be seen that gained catalyst weight-loss ratio is 72.12%, shows that its stability is good
Good.
NH from Fig. 53CO in temperature programming desorption collection of illustrative plates and Fig. 62Temperature programming desorption collection of illustrative plates, it can be seen that implement
Catalyst prepared by example 1 shows acidic character peak and basic character peak simultaneously.
Prepared macropore soda acid difunctional organic solid catalyst is carried out catalytic test and regeneration test, and result shows: fiber
The conversion ratio of element is 41.2%, is to improve a lot compared with in the of 32% with the conversion ratio of the most single acidic catalyst；Catalyst
In regenerative process, the conversion ratio of cellulose is followed successively by 40.9%, 40.5%, 40% and 39.2%, and regeneration effect is preferable.
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 and forms mixed solution in 4mL deionized water as aqueous phase, mechanical agitation 25 points
It is made to mix after clock.Taking the paraffin of 36mL as oil phase, under ceaselessly mechanical agitation, oil phase is added dropwise to
Aqueous phase mixes, stirs 15min, be prepared as stable HIPEs.
(2) it is warming up to 50 DEG C of holdings and within 15 hours, carries out thermal-initiated polymerization reaction, through acetone through surname extraction eluting surface activating agent
And paraffin, products therefrom is dried under 52 DEG C of vacuum 22h, obtains polymer.
(3) configure the salpeter solution of 1.2mol/L, take the 50mL nitre that after 0.5g polymer is ground into powder, addition is configured
In acid solution, stir 22h, at 75 DEG C, be vacuum dried 20h, obtain macropore solid acid alkali catalytic agent.
Prepared macropore soda acid difunctional organic solid catalyst is carried out catalytic test and regeneration test, and result shows: fiber
Element conversion ratio is 38.7%, is to improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst；Catalyst regeneration process
In, cellulose conversion ratio is followed successively by 38.7%, 38.5%, 38.1% and 37.9%, and regeneration effect is preferable.
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 and forms mixed solution in 4.64g deionized water as aqueous phase, mechanical agitation 30
It is made to mix after minute.Taking the paraffin of 41.76mL as oil phase, under ceaselessly mechanical agitation, oil phase dropwise adds
Entering in aqueous phase mixing, mechanical agitation, after 20 minutes, is prepared as stable HIPEs.
(2) it is warming up to 85 DEG C of holdings and within 26 hours, carries out thermal-initiated polymerization reaction, through acetone through surname extraction eluting surface activating agent
And paraffin, products therefrom is dried under 55 DEG C of vacuum 24h, obtains polymer.
(3) configure the hydrochloric acid solution of 1.36mol/L, take the 50mL sulphur that after 0.64g polymer is ground into powder, addition is configured
In acid solution, stir 24h, at 80 DEG C, be vacuum dried 22h, obtain macropore solid acid alkali catalytic agent.
Prepared macropore soda acid difunctional organic solid catalyst is carried out catalytic test and regeneration test, and result shows: fiber
Element conversion ratio is 39.9%, is to improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst；Catalyst regeneration process
In, cellulose conversion ratio is followed successively by 39.5%, 38.9%, 38.1% and 37.7%, and regeneration effect is preferable.
Embodiment 4:
(1) by 1.3g p styrene sulfonic acid, 0.34g acrylamide, 0.04g potassium peroxydisulfate, 0.031g N, N-di-2-ethylhexylphosphine oxide third
Acrylamide, 0.04g Tween 85 joins formation mixed solution in 4g deionized water and makes after 30 minutes as aqueous phase, mechanical agitation
It mixes.Taking the paraffin of 35mL as oil phase, under ceaselessly mechanical agitation, oil phase is added dropwise in aqueous phase
Mixing, mechanical agitation, after 20 minutes, is prepared as stable HIPEs.
(2) it is warming up to 65 DEG C of holdings and within 24 hours, carries out thermal-initiated polymerization reaction, through acetone through surname extraction eluting surface activating agent
And paraffin, products therefrom is dried under 55 DEG C of vacuum 24h, obtains polymer.
(3) configure the sulfuric acid solution of 1mol/L, take the 50mL sulfuric acid that after 0.5g polymer is ground into powder, addition is configured
In solution, stir 24h, at 80 DEG C, be vacuum dried 24h, obtain macropore solid acid alkali catalytic agent.
Prepared macropore soda acid difunctional organic solid catalyst is carried out catalytic test and regeneration test, and result shows: fiber
Element conversion ratio is 42.1%, is to improve a lot compared with in the of 32% with the conversion ratio of single acidic catalyst；Catalyst regeneration process
In, cellulose conversion ratio is followed successively by 42.1%, 41.9%, 41.7% and 41.5%, and regeneration effect is preferable.
Described embodiment be the present invention preferred embodiment, but the present invention is not limited to above-mentioned embodiment, without departing substantially from this
In the case of the flesh and blood of invention, any conspicuously improved, replacement or modification that those skilled in the art can make are equal
Belong to protection scope of the present invention.
Claims (8)
1. the preparation method of a macropore soda acid difunctional organic solid catalyst, it is characterised in that comprise the steps of
(1) by p styrene sulfonic acid, water miscible polymerizable alkaline monomer, initiator, N,N methylene bis acrylamide and breast
Agent adds in deionized water, and as aqueous phase, stirring makes it mix；Take paraffin as oil phase, under being stirred continuously dropwise
Add in aqueous phase, be prepared as stable High Internal Phase Emulsion；Described deionized water, p styrene sulfonic acid, water miscible polymerizable alkali
The mass ratio of property monomer, initiator, N,N methylene bis acrylamide 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)；Described paraffin and deionization
The volume ratio of water is (30.24-41.76): (3.36-4.64)；
(2) High Internal Phase Emulsion described in step (1) is warming up to 60-85 DEG C keeps 15-26h to carry out thermal-initiated polymerization reaction,
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, through filtration, deionized water
Macropore soda acid difunctional organic solid catalyst is i.e. obtained after washing, vacuum drying.
The preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst, it is characterised in that step
Suddenly water miscible polymerizable alkaline monomer described in (1) is acrylamide or 1-vinyl imidazole, and initiator is potassium peroxydisulfate or mistake
Ammonium sulfate, emulsifying agent is sorbitan monooleate APEO (Tween80) or polyoxyethylene sorbitol acid anhydride three oleic acid
Ester (Tween85).
The preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst, it is characterised in that step
Suddenly described in (2), the temperature of polymerisation is 60-65 DEG C, and the time is 18-24h.
The preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst, it is characterised in that step
Suddenly dilute acid soln described in (3) is the dilute sulfuric acid of 0.64-1.36mol/L, dust technology or watery hydrochloric acid, polymer and dilute acid soln
Solid-to-liquid ratio is (0.36-0.64) g:50mL.
The preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst, it is characterised in that step
Suddenly described in (2), vacuum drying temperature is 50-55 DEG C, and the time is 20-24h.
The preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst, it is characterised in that step
Suddenly described in (3), vacuum drying temperature is 70-80 DEG C, and the time is 20-24h.
The macropore soda acid prepared by preparation method of macropore soda acid the most according to claim 1 difunctional organic solid catalyst
Difunctional organic solid catalyst.
Macropore soda acid the most according to claim 7 difunctional organic solid catalyst is applied to catalysis fibre element and is degraded to 5-
The reaction of hydroxymethylfurfural.
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| CN105642345B (en) * | 2015-04-03 | 2018-08-10 | 江苏大学 | A kind of preparation method of hydrophobic multi-stage porous solid acid-base bifunctional catalyst |
| CN105289540B (en) * | 2015-11-11 | 2017-07-18 | 江苏大学 | A kind of method for preparing porous difunctional sorbing material |
| CN105514348B (en) * | 2016-01-18 | 2017-12-01 | 方倩 | A kind of preparation method of zinc electrode used for zinc-air battery |
| CN106111194B (en) * | 2016-06-22 | 2018-10-09 | 江苏大学 | A kind of preparation method of the solid multistage pore catalyst containing Br*nsted and Lewis acid |
| CN106311345A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Acid-base bifunctional solid catalyst and preparation method thereof |
| CN106366221A (en) * | 2016-08-07 | 2017-02-01 | 刘天泽 | Preparation method for amino-functionalized macroporous styrene resin with large specific surface |
| CN107142255A (en) * | 2017-05-31 | 2017-09-08 | 桂林理工大学 | A kind of method of the phase pickering emulsions as templated synthesis immobilised enzymes material using in height |
| CN108970592B (en) * | 2018-07-20 | 2021-07-13 | 江苏科技大学 | Preparation method and application of sulfonic acid type silver porous adsorbent for ion adsorption |
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