CN104984758A - Frozen gel catalyst, preparation method and applications thereof - Google Patents
Frozen gel catalyst, preparation method and applications thereof Download PDFInfo
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- CN104984758A CN104984758A CN201410704491.8A CN201410704491A CN104984758A CN 104984758 A CN104984758 A CN 104984758A CN 201410704491 A CN201410704491 A CN 201410704491A CN 104984758 A CN104984758 A CN 104984758A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The present invention relates to a frozen gel catalyst, a preparation method and applications thereof. According to the present invention, the catalyst substrate is a polyacrylamide frozen gel, the catalyst contains at least an alkaline group, the catalyst contains at least an acidic group, or the catalyst concurrently contains at least an acidic group and at least an alkaline group; the defects of short catalyst service life, environmental pollution, high energy consumption, batch reproducibility and the like of the transesterification reaction are overcome; and the catalyst is a polymer catalyst, the appearance presents the loose frozen gel (cryogel) structure, and the catalyst concurrently contains the acidic group and the alkaline group, can catalyze ester bond hydrolysis, peptide bond hydrolysis and transesterification, and is an efficient catalyst for biodiesel production.
Description
Technical field
The invention belongs to new material, catalysis, chemical industry and new energy field, particularly a kind of ice glue Catalysts and its preparation method and application.
Background technology
Along with the minimizing of fossil energy reserves and the increase of environmental pollution, sustainable, the eco-friendly alternative fuel of developing green has become one of most important research topic of the mankind.Biodiesel, as the clean liquid bio-fuel of alternative petrifaction diesel, has huge potentiality and wide market prospects.
Before the present invention makes, what current production biodiesel adopted is transesterification or ester exchange reaction, namely directly react by the low-carbon alcohols such as methyl alcohol or ethanol and aliphatic acid, or exchange with fatty glyceride, generate corresponding fatty acid methyl ester or fatty-acid ethyl ester.Usual ester exchange reaction is the comparatively convenient method obtaining biodiesel.
Ester exchange reaction used catalyst can be divided into acidic catalyst, base catalyst, biological enzyme agent etc.Wherein acidic catalyst comprises sulfuric acid, sulfonic acid and various solid acid catalyst.Strongly acidic cation-exchange and phosphate are typical solid acid catalysts.Because acid catalyzed reaction speed is lower, need higher temperature and longer reaction time, and the service life of catalyst is short, because which limit commercial Application.
Base catalyst is most popular catalyst in current production biodiesel, is mainly divided into two large classes: (1) liquid-phase catalyst (being dissolved in methyl alcohol): KOH, NaOH, NaOCH
3deng; (2) solid base catalyst: strong-base anion-exchange resin, molecular sieve, alkali (soil) metal oxide, carbonate etc.
The catalyst amounts such as potassium hydroxide, NaOH, sodium methoxide are about 1%, and about reaction temperature fixes on the boiling point of methyl alcohol, reaction is fast, conversion ratio is high.After this type of catalytic reaction completes, product neutralization, washing can produce a large amount of industrial wastewaters, cause environmental pollution or intractability is strengthened.
Insoluble solid base catalyst can solve the problem that product is separated with catalyst difficulty.Strong-base anion-exchange resin has reaction condition gentleness, feature that conversion ratio is high as the catalyst of ester exchange reaction, catalyst have be convenient to separation and recovery, can reuse, not polluted product, byproduct glycerine is also easier to be separated.Shortcoming is that the activation of resin needs repeatedly to soak with soda acid, and regeneration step need to improve; Resin anion (R.A.) can only use below 60 DEG C in addition, otherwise will soon inactivation, and under low temperature, ester exchange activity is lower, which has limited its using value.Hydrotalcite-like anionic clays has basic active center, is another kind of important solid base catalyst.The Mg-Al composite oxides that calcined hydrotalcite obtains are a kind of mesopore materials, have layer structure, have bigger serface and high stability, and alkalescence is stronger and adjustable.The molecular sieve of special synthesis can use as catalyst for ester exchange reaction.But also there is the problems such as the high and batch reproducibility of energy consumption in these synthetic inorganic materials.
Summary of the invention
The object of the invention is to overcome above-mentioned defect, development ice glue Catalysts and its preparation method and application.
Technical scheme of the present invention is:
A kind of ice glue catalyst, its technical characteristics is: (1) catalyst matrix is polyacrylamide ice glue; (2) catalyst is at least containing a kind of basic group; (3) catalyst is at least containing a kind of acidic-group, or (4) catalyst is simultaneously containing at least one acidic-group and a kind of basic group.
Described acidic-group is carboxylate radical or sulfonate radical.
Described basic group is amino.
Described acidic-group comes from following monomer or its mixture: acrylic acid or its salt, methacrylic acid or its salt, alpha-cyanoacrylate or its salt, aconitic acid or its salt, fumaric acid or its salt, maleic acid or its salt, allyl sulphonic acid or its salt, 2-acrylamido-2-methyl propane sulfonic acid or its salt; Described basic group comes from following monomer or its mixture: vinylamine, N-methyl methylene amine, dimethyl propylene thiazolinyl amine, allyl amine, diallylamine, triallylamine.
Another technical scheme of the present invention is:
A preparation method for ice glue catalyst, its technical characteristics is that step is as follows:
(1) pre-polymer solution is prepared: acrylamide, N, the mixed solution of N '-methylene-bisacrylamide, toward wherein adding acidity, alkaline monomer or their mixture, be uniformly mixed ultrasonic degas, add polymerization initiator, again mix, ultrasonic degas;
(2) polymerisation: carry out polymerisation under pre-polymer solution being placed in freezing conditions;
(3) polymer washing, dry: polymer is removed the inorganic salts that unreacted monomer and initator bring through thawing, washing, finally obtain acidity, alkalescence and both sexes ice xanthan polymer, polymer obtains catalyst after super-dry.
The another technical scheme of the present invention is:
An application for ice glue catalyst, its technical characteristics is: described catalyst can the hydrolysis of catalysis ester class and ester exchange reaction.
Described catalyst can the hydrolysis of catalytic proteins.
Described catalyst can catalyze fatty acid methyl esters, fatty-acid ethyl ester synthesis.
Described catalyst is used for catalytically synthesizing biological diesel oil.
Advantage of the present invention and effect are to provide a family macromolecule catalyst, its outward appearance is presented as loose ice glue (cryogel) structure, simultaneously containing acid and basic group on catalyst, can catalysis ester bond, the hydrolysis of peptide bond and ester exchange reaction, be a kind of effective catalyst producing biodiesel.
Accompanying drawing explanation
The digital photograph schematic diagram of ice xanthan polymer in Fig. 1---embodiment 1.
The scanning electron microscope (SEM) photograph of ice xanthan polymer in Fig. 2---embodiment 1.
Ice glue catalyst protein hydrolysate electrophoretogram in Fig. 3---embodiment 7.
Detailed description of the invention
Technical thought of the present invention is:
The first step: preparation pre-polymer solution.Acrylamide, N, the mixed solution of N '-methylene-bisacrylamide, toward wherein adding acidity, alkaline monomer or their mixture, mixed by electromagnetism or mechanical agitation, ultrasonic degas (main purpose be remove oxygen molecule), in order to avoid the living radical that quencher produces subsequently.Add polymerization initiator, again mix, ultrasonic degas, object is to remove oxygen molecule equally.
Second step: polymerisation.Pre-polymer solution is placed in refrigerator cabinet freezer (-20 DEG C), carries out polymerisation in ice conditions 24 hours.In ice conditions, in pre-polymer solution, part water build-ups ice, and occupy large quantity space, monomer mixture is closed, be confined in narrow space, this part solution was compared with originally, and volume greatly reduces, and therefore in fact monomer concentration improve several times than originally.The polymer formed in these cases is no longer water imbibition gel, but loose porous ice glue.
3rd step: polymer washing, drying.The polymer that obtained by second step removes the inorganic salts that unreacted monomer and initator bring through thawing, washing, finally obtain acidity, alkalescence and both sexes ice xanthan polymer.
4th step: the application of polymer.This base polymer has loose and porous structure, large with liquid comes into contact specific surface, easy infiltration, polymer contain acidity, basic group or contain two kinds of groups simultaneously, there is catalytic proteins hydrolysis, ester-type hydrolysis and ester exchange reaction activity (because namely the chemical nature of enzymatic protein hydrolysis, ester-type hydrolysis is acid (alkali) catalysis), can be used as catalyst and use.
The present invention can be elaborated further by following examples, but not as limitation of the present invention.
Embodiment 1:
In 800mL distilled water, add 15g acrylamide, 7.5g N, N '-methylene-bisacrylamide, 2.5mL acrylic acid, 2.5mL allyl amine, ultrasonic degas 5min, obtain pre-reaction mixed solution.In mixed solution, add 2g ammonium persulfate and 0.8g sodium hydrogensulfite, mixture aqueous solution is put into water-bath (40-50 DEG C) and cause 5 minutes, then reaction mixture is put into refrigerator (-20 DEG C) and continue polymerization more than 24h.Rinse with distilled water concussion the ice xanthan polymer (Fig. 1) obtained after thawing.Extracted by water in polymer, putting into baking oven 60 DEG C of dryings, namely to can be used as catalyst stand-by.Fig. 2 is polymer scanning electron microscope (SEM) photograph.Process that is acid by other, alkaline monomer mixture synthetic catalyst is similar.
Embodiment 2:
In 800mL distilled water, add 15g acrylamide, 7.5g N, N '-methylene-bisacrylamide, 2.5mL allyl amine, ultrasonic degas 5min, obtain pre-reaction mixed solution.In mixed solution, add 2g ammonium persulfate and 0.8g sodium hydrogensulfite, mixture aqueous solution is put into water-bath (40-50 DEG C) and cause 5 minutes, then afterwards reaction mixture is put into refrigerator (-20 DEG C) and continue polymerization more than 24h.Rinse with distilled water concussion the ice xanthan polymer (Fig. 1) obtained after thawing.Extracted by water in polymer, putting into baking oven 60 DEG C of dryings, namely to can be used as catalyst stand-by.Similar by the process of other alkalescence monomers or alkaline monomer mixture synthetic catalyst.
Embodiment 3:
In 800mL distilled water, add 15g acrylamide, 7.5g N, N '-methylene-bisacrylamide, 2.5mL acrylic acid, ultrasonic degas 5min, obtain pre-reaction mixed solution.In mixed solution, add 2g ammonium persulfate and 0.8g sodium hydrogensulfite, mixture aqueous solution is put into water-bath (40-50 DEG C) and cause 5 minutes, then afterwards reaction mixture is put into refrigerator (-20 DEG C) and continue polymerization more than 24h.Rinse with distilled water concussion the ice xanthan polymer (Fig. 1) obtained after thawing.Extracted by water in polymer, putting into baking oven 60 DEG C of dryings, namely to can be used as catalyst stand-by.Similar by the process of other acidity monomers or acid monomer mixture synthetic catalyst.
Embodiment 4:
Ester exchange reaction.Olein: methyl alcohol ratio is 1: 2 (mol ratio), the addition of polyalcohol catalyst is 2.0% of oily-ol mixture quality, be sealed in 5mL plastic tube after mixing, take out after being placed in 40 DEG C of water bath with thermostatic control shaking table oscillating reactions certain hours, centrifugal 10 minutes of 3000r/min, gets upper strata sample for analyzing conversion ratio etc.
Embodiment 5:
The synthesis of biodiesel.Rich mixture: methanol quality is than 2: 1, the addition of polyalcohol catalyst is 2.0% of oily-ol mixture quality, be placed in 5L glass reaction still, electric jacket heats, maintain reflux state, pumped lower floor's glycerine every 1 hour, no longer include glycerine after 4-14 hour and generate, after removing unnecessary methyl alcohol, obtain fatty acid methyl ester (biodiesel).
Embodiment 6:
Utilize Micellar Electrokinetic Capillary Chromatographic Analysis ester exchange reaction
Take SDS (lauryl sodium sulfate), the borax of certain mass respectively, dissolve with distilled water, add appropriate normal octane, n-butanol, methyl alcohol, with distilled water constant volume in 50mL volumetric flask, stand-by as mobile phase, its optium concentration is respectively SDS:120mM; Borax: 10mM; Normal octane: 60mM; N-butanol: 324mM.Separation condition: methyl alcohol volume fraction 2%, voltage :-18kv, UV detect wavelength is 210nm, adopts positive and negative electrode discrepancy in elevation sample introduction (9cm, 10s).Capillary column length 50cm (50 μm of i.d., 38cm effective lengths).With the NaOH of 100mM, capillary is rinsed between every twice sampling interval, and balance with cushioning liquid.Internal standard compound is ethylo benzene (2.0%, v/v), carries out quantitatively, thus calculate ester interchange conversion rate according to calculated by peak area.
Embodiment 7:
Ice glue catalyst proteolysis
Hemoglobin (people) is dissolved in the Tris-HCL buffer solution (pH 7.5) of 25mM, is made into the solution of 2.0mg/mL.In protein solution, add the polyalcohol catalyst of 10% (quality), shake up, be placed in 37 DEG C of water-bath incubations 1 hour.Get solution before and after enzymolysis to analyze.Capillary Electrophoresis condition is: capillary column: 75 μm of i.d. × 42cm (effective length 34cm).Mobile phase: Tris-HCL buffer solution (pH 7.5).Sample introduction: 10.0kV 5s.Separation voltage: 10.0kV.Determined wavelength: 214nm.Result is as Fig. 3, and hemoglobin demonstrates unimodal, through enzymolysis, obtains different peptide section, and the number showing as peak increases.Protein digestion is be conducive to qualitative and quantitative analysis after peptide section.
Claims (9)
1. an ice glue catalyst, is characterized in that: (1) catalyst matrix is polyacrylamide ice glue; (2) catalyst is at least containing a kind of basic group; (3) catalyst is at least containing a kind of acidic-group, or (4) catalyst is simultaneously containing at least one acidic-group and a kind of basic group.
2., according to ice glue catalyst a kind of described in claim 1, it is characterized in that: described acidic-group is carboxylate radical or sulfonate radical.
3. according to ice glue catalyst a kind of described in claim 1, it is characterized in that: described basic group is for amino.
4. according to ice glue catalyst a kind of described in claim 1, it is characterized in that: described basic group comes from following monomer or its mixture for the acidic-group described in amino: acrylic acid or its salt, methacrylic acid or its salt, alpha-cyanoacrylate or its salt, aconitic acid or its salt, fumaric acid or its salt, maleic acid or its salt, allyl sulphonic acid or its salt, 2-acrylamido-2-methyl propane sulfonic acid or its salt; Described basic group comes from following monomer or its mixture: vinylamine, N-methyl methylene amine, dimethyl propylene thiazolinyl amine, allyl amine, diallylamine, triallylamine.
5. a preparation method for ice glue catalyst, is characterized in that step is as follows:
(1) pre-polymer solution is prepared: acrylamide, N, the mixed solution of N '-methylene-bisacrylamide, toward wherein adding acidity, alkaline monomer or their mixture, be uniformly mixed ultrasonic degas, add polymerization initiator, again mix, ultrasonic degas;
(2) polymerisation: carry out polymerisation under pre-polymer solution being placed in freezing conditions;
(3) polymer washing, drying: by polymer through thawing, washing and remove unreacted monomer and initator, finally obtain acidity, alkalescence and both sexes ice xanthan polymer, polymer obtains catalyst after super-dry.
6. an application for ice glue catalyst, is characterized in that: described catalyst can the hydrolysis of catalysis ester class and ester exchange reaction.
7. according to a kind of described in claim 6 application of ice glue catalyst, it is characterized in that: described catalyst can the hydrolysis of catalytic proteins.
8., according to a kind of described in claim 6 application of ice glue catalyst, it is characterized in that: described catalyst can catalyze fatty acid methyl esters, fatty-acid ethyl ester synthesis.
9. according to a kind of described in claim 8 application of ice glue catalyst, it is characterized in that: described catalyst is used for catalytically synthesizing biological diesel oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693922A (en) * | 2016-02-02 | 2016-06-22 | 扬州大学 | Amphiprotic protein ice gel imprinted polymer, and preparation method and application thereof |
| CN106423097A (en) * | 2016-10-12 | 2017-02-22 | 扬州大学 | Method for processing activated dyes through combination of frozen gel adsorbing material and non-water electrolysis method |
| CN108217814A (en) * | 2018-02-12 | 2018-06-29 | 浙江工业大学 | A kind of method using brilliant glue adsorption treatment on sewage |
-
2015
- 2015-08-12 CN CN201410704491.8A patent/CN104984758A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| CHUN YANG 等: "Polyacrylamide Based Cryogels as Catalysts for Biodiesel", 《CATAL LETT》 * |
| 杨春 等: "冰胶印迹聚合物固定化脂肪酶的制备及催化性能", 《现代化工》 * |
| 杨春 等: "待定模版印迹聚合物对高丰度鸡蛋清蛋白质的脱除", 《分析化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693922A (en) * | 2016-02-02 | 2016-06-22 | 扬州大学 | Amphiprotic protein ice gel imprinted polymer, and preparation method and application thereof |
| CN106423097A (en) * | 2016-10-12 | 2017-02-22 | 扬州大学 | Method for processing activated dyes through combination of frozen gel adsorbing material and non-water electrolysis method |
| CN106423097B (en) * | 2016-10-12 | 2019-03-29 | 扬州大学 | A kind of method of ice glue adsorbent material and non-aqueous solution electrolysis method combination processing reactive dye |
| CN108217814A (en) * | 2018-02-12 | 2018-06-29 | 浙江工业大学 | A kind of method using brilliant glue adsorption treatment on sewage |
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Application publication date: 20151021 |