CN103977781A - Preparation method of porous heterogeneous base catalyst and applications of catalyst - Google Patents
Preparation method of porous heterogeneous base catalyst and applications of catalyst Download PDFInfo
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- CN103977781A CN103977781A CN201410227196.8A CN201410227196A CN103977781A CN 103977781 A CN103977781 A CN 103977781A CN 201410227196 A CN201410227196 A CN 201410227196A CN 103977781 A CN103977781 A CN 103977781A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention discloses a preparation method of a porous heterogeneous base catalyst and applications of the catalyst, relating to field of material chemistry and a catalyst and preparation thereof. The preparation method comprises the following steps: reacting with acid to produce calcium slat by taking calcium-based calcite ores rich in calcium carbonate as raw materials, then mixing the calcium salt with the template agents according to the mass ratio of 1:0.5-1:10 by taking carbohydrates and sucrose derivatives as template agents,, adjusting the pH of the reaction system to be 2-7 through organic base by taking alcohol substances as a solvent,, heating and stirring and reacting for 0.5-6 hours, aging and gelling in a drying oven at 25-100DEG C, finally calcining and activating in a tubular furnace and then cooling, thus obtaining the porous out-of-phase base catalyst with higher specific surface area and pore volume. The porous heterogeneous base catalyst is used for catalyzing active ingredients animal and plant oil to have transesterification reaction with methanol or ethanol to prepare biodiesel oil. Compared with the manner of directly calcining calcite as a catalyst, the modified calcite catalyst prepared by adopting the method is used for catalyzing the transesterification reaction, and the catalytic activity under the same reaction condition can be improved by more than 40%.
Description
Technical field
The present invention relates to materials chemistry and catalyst and preparation field thereof, specifically, is a kind of preparation method of porous out-phase base catalyst and the purposes of this catalyst.
Background technology
Along with the development of World Economics, the demand of traditional fossil energy increases year by year, and the greenhouse effects that the use of energy security and traditional fossil energy produces become the problem of global concern.Biodiesel because it is renewable, safe, biological degradability is high, sulfur content is low, do not receive gradually people's concern containing aromatic hydrocarbon, the advantage such as nontoxic.Owing to having, catalyst can be recycled heterocatalysis technique, product is easily separated, avoid the advantage that produces a large amount of waste water to be subject to extensive concern in recent years, and especially preparing different-phase catalyst taking richness cheap natural minerals calciferous as raw material is one of focus of biodiesel preparation research in recent years.
The advantages such as CaO has active high, and price is low, and alkalescence is strong, become study hotspot in recent years just gradually.Liu etc.
[1]preparing biodiesel with commercially available CaO catalysis soybean oil and methyl alcohol ester exchange reaction, is being 12:1 at molar ratio of methanol to oil, and catalyst amount is 8wt%, 65 DEG C of reaction 3h, and fatty acid methyl ester conversion rate is higher than 80%.Natural calcium foundation stone material is more and more subject to people's attention because of cheap and easy to get as calcite, dolomite etc.
[2].Wilson etc.
[3]with the natural dolomite catalyzed transesterification of 800 DEG C of calcinings, result shows: calcining natural calcite is at catalysis C
4, C
8even long-chain C
16-18in ester exchange reaction Deng triglyceride and methyl alcohol, show very high catalytic activity.Yoosuk etc.
[4]adopt aquation-evaporation taking dolomite as raw material, Kaolinite Preparation of Catalyst, catalysis palm oil and Methanol are for biodiesel.By controlling aquation-dehydration modification dolomite, be 10:1 at molar ratio of methanol to oil, catalyst amount is 3wt%, 60 DEG C of reaction 1.5 h, fatty acid methyl ester conversion rate reaches 93.3%, however its reuse 5 times after fatty acid methyl ester die-off.Ngamcharussrivichai etc.
[5]at adopting 800 DEG C, the calcite catalysis palm oil of calcining reacts preparation biodiesel with methyl alcohol.And investigated 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C different calcining heats, on the impact of calcining calcite catalyst B ET specific area.Result shows, calcine rear calcite specific area and obviously increase, and after calcining at 800 DEG C, its specific area is up to 19.58 m
2/ g.Be 30:1 at molar ratio of methanol to oil, catalyst amount is 6wt%, 60 DEG C of reaction 3h, and fatty acid methyl ester productive rate can reach 98wt%, and catalyst is relatively stable, reuses after 10 times, and its fatty acid methyl ester productive rate is higher than 80wt%.Yoosuk etc.
[6]deng employing aquation-evaporation, taking calcite as raw material Kaolinite Preparation of Catalyst, catalysis palm oil and Methanol are for biodiesel.Be 15:1 at molar ratio of methanol to oil, catalyst amount is 7wt%, 60 DEG C of reaction 0.75h, and fatty acid methyl ester brings up to 93.9% from 75.5wt.%, and catalyst is more stable, reuses after 5 times, and its fatty acid methyl ester is still not less than 90 wt%.Wang etc.
[7]with stearic acid modified calcite, under the air stream of 50L/h, calcine 1h at 750 DEG C, then close air stream, be warming up to 850 DEG C of modification calcite catalyst of calcining again 1h and obtaining meso-hole structure.Dinectly bruning calcite BET specific area is only 4.1m
2/ g, after calcining, porous calcite BET specific area increases to 8.7m
2/ g.Be 10:1 at molar ratio of methanol to oil, catalyst amount is 3wt%, 65 DEG C of reaction 3h, and fatty acid methyl ester is up to 98wt%, but this catalyst is unstable, and its loose structure easily caves in, and reusability is bad.
Summary of the invention
Object of the present invention, high for current CaO catalysis for preparing biodiesel oil cost, the drawbacks such as activity is low and dinectly bruning calcite specific area are less, the present situation that catalytic transesterification activity is lower and catalyst reusability is poor, propose a kind of simple to operate, the preparation method of the cheap catalyst with greater catalytic efficiency, the out-phase base catalyst specific area and the pore volume that prepare are all larger, catalyzed transesterification activity has improved 40% compared with dinectly bruning calcite, and after catalyst recovery, do not need other any washing process, dinectly bruning activation is just reusable.
The preparation method of a kind of porous out-phase of the present invention base catalyst, taking richness calcium base calciferous calcite ore as raw material, generate calcium salt with acid reaction, again with monose, disaccharide, compound sugar or polysaccharide glucide or carbohydrate derivative are template, be that 1:0.5～1:10 ratio is mixed above-mentioned calcium salt and template in mass ratio, with methyl alcohol, ethanol or ethylene glycol are solvent, regulate reaction system pH as 2～7 taking organic base, at 25～150 DEG C of stirring reaction 0.5～6h, be transferred to while hot again in porcelain boat, 25～100 DEG C of ageing 24～120h gels in baking oven, finally calcining and activating 1～5h in the tube furnace of 600～850 DEG C, cooling in drier, can obtain the porous out-phase base catalyst of high specific surface area and pore volume.
onstating monosaccharide and disaccharide, compound sugar or polysaccharide glucide is glucose, fructose, ribose, deoxyribose, sucrose, maltose, lactose, cyclodextrin, starch, glycogen, cellulose, hemicellulose, chitin or proteoglycans; The derivative of above-mentioned sugar is sugar alcohol, saccharic acid, osamine, glucosides; Above-mentioned template is one or more templates that mix in glucide or carbohydrate derivative.
In above-mentioned template, glucide is preferably sucrose, glucose, soluble starch.
Above-mentioned reaction acid used is HNO
3, HCl, HCOOH or CH
3cOOH.
Above-mentioned reaction organic base used is ammoniacal liquor, ethylenediamine, triethylamine, pyridine.
In above-mentioned tube furnace, the condition of calcining and activating is under vacuum or condition of normal pressure, under the atmospheric condition of air stream, nitrogen stream or argon gas stream, activates.
The application of porous out-phase base catalyst of the present invention is the catalyst that the vegetable and animals oils that is fatty acid triglycercide for catalysis main component and methyl alcohol or ethanol ester exchange reaction are prepared biodiesel.
Porous out-phase base catalyst of the present invention is reusable, its renovation process be reacted catalyst after centrifugation, in tube furnace, 600～800 DEG C of calcining and activatings, reusable.
Characterize (Fig. 1) by SEM visible, dinectly bruning Calcite Surface is formed by inhomogenous particle packing, and between particle, there is very large space, and the porous catalyst of preparing as template taking glucose, sucrose, soluble starch, beta-schardinger dextrin-(Fig. 2-a, 2-b, 2-c, 2-d),, by uniform spherical granule composition, there is obvious pore passage structure on surface.By the N to dinectly bruning calcite and glucose, sucrose, soluble starch, beta-schardinger dextrin-template modified catalyst
2adsorption-desorption characterization result shows, the specific area of dinectly bruning calcite catalyst is 3.5m
2/ g, and be respectively 20.2m with the specific area of the calcite catalyst of glucose, sucrose, soluble starch, the modification of beta-schardinger dextrin-template
2/ g, 27.4 m
2/ g, 16.5 m
2/ g, 6.6 m
2/ g.
As seen from Figure 3, under equivalent responses condition, calcite (CC) through the catalyzed transesterification activity of the porous calcite of glucose (CG), sucrose (CS), soluble starch (CSS), beta-schardinger dextrin-(CCD) modification apparently higher than dinectly bruning, and the highest with the catalyst activity of sucrose modification.
Brief description of the drawings
The micro-Electronic Speculum figure of scanning of Fig. 1 dinectly bruning calcite.Illustrate that dinectly bruning Calcite Surface is formed by inhomogenous particle packing, and have very large space between particle.
The micro-Electronic Speculum figure of scanning of Fig. 2 modification calcite, (a) through glucose modified gained calcining porous calcite; (b) through sucrose modification gained calcining porous calcite; (c) through soluble starch modification gained calcining porous calcite; (d) through beta-schardinger dextrin-modification gained calcining porous calcite.Illustrate that glucose, sucrose, soluble starch, beta-schardinger dextrin-are that porous catalyst surface prepared by template forms by uniform spherical granule, have obvious pore passage structure.
The active comparison diagram of the various catalyst ester exchanges of Fig. 3, wherein CC be dinectly bruning calcite, CG for the glucose modified calcite of calcining, CS for calcining sucrose modification calcite, CSS for calcining soluble starch modification calcite, CCD be calcination of beta-cyclo-dextrin-modified calcite.(reaction condition: jatropha curcas oil 3.0g, catalyst amount: 0.06 g(2wt%) methyl alcohol/molar equivalent: 8:1, reaction time 90min, 65 DEG C of oil bath temperatures).Illustrate that carbohydrate molecule modification calcite catalyst activity is higher than CC.
Fig. 4 soluble starch modification calcite catalyst reuse number of times.Illustrate that modified catalyst is through reusing 5 times, catalytic activity is substantially constant
Fig. 5 is the micro-Electronic Speculum figure of scanning of the soluble starch modified catalyst after regeneration activating for the second time.Illustrate that regenerated catalyst and Fig. 2-c structure are similar, after this catalyst regeneration, structure does not change, stable in properties.
Detailed description of the invention
Embodiment mono-,
1. the preparation of catalyst.Get 1g calcite powder in round-bottomed flask, add a certain amount of 10% HNO
3the aqueous solution dissolves, to solution clarification, stirring at room temperature adds the ethylene glycol solution of 1.98g soluble starch and 10mL, and with ammoniacal liquor regulation system, pH is about 2 left and right, after 80 DEG C of stirring reaction 120min, be transferred to while hot in porcelain boat, ageing 96h gel in 40 DEG C of baking ovens then after 750 DEG C of calcining and activating 120min, takes out and puts into immediately vacuum desiccator while hot in tube furnace, must calcine modified porous calcite out-phase base catalyst, for subsequent use.
2. catalyzed transesterification.Take acid number lower than the barbadosnut seed oil 10g of 1mgKOH/g in 50mL round-bottomed flask, add absolute methanol 2.80g, then add the glucose modified catalyst of 0.20g, back flow reaction 90min.Product is removed methyl alcohol, after a small amount of glycerine of centrifugation, is obtained Bio-diesel Samples again through centrifugation catalyst and, decompression distillation, and obtaining fatty acid methyl ester through gas phase analysis is 98.1%, and productive rate is 86.3%.
3. the regeneration of catalyst.Reacted catalyst, after centrifugation, is not needed to complicated aftertreatment technology, and directly 700 DEG C of calcining and activating 120min in tube furnace, reusable.
Embodiment bis-,
1. the preparation of catalyst.Get 1g calcite powder in round-bottomed flask, add a certain amount of 10% HCl aqueous solution to dissolve, to solution clarification, stirring at room temperature adds the absolute methanol solution of 1.98g Dextrose Monohydrate and 10mL, with ammoniacal liquor regulation system, pH is about 4 left and right, after 60 DEG C of stirring reaction 180min, be transferred to while hot in porcelain boat, ageing 48h gel in 60 DEG C of baking ovens, then in tube furnace after 800 DEG C of calcining and activating 150min, take out and put into immediately vacuum desiccator while hot, must calcine modified porous calcite out-phase base catalyst, for subsequent use.
2. catalyzed transesterification.Ester exchange reaction method is with embodiment mono-, and obtaining fatty acid methyl ester through gas phase analysis is 90.1%, and productive rate is 81.6%.
3. the regeneration of catalyst.The renovation process of catalyst is with embodiment mono-.
Embodiment tri-,
1. the preparation of catalyst.Get 1g calcite powder in round-bottomed flask, add a certain amount of HCOOH solution to dissolve, stirring at room temperature adds the ethanol solution of 3.42g sucrose and 10mL, and with ammoniacal liquor regulation system, pH is about 6 left and right, after 50 DEG C of stirring reaction 210min, be transferred to while hot in porcelain boat, ageing 72h gel in 80 DEG C of baking ovens then after 800 DEG C of calcining and activating 120min, takes out and puts into immediately vacuum desiccator while hot in tube furnace, must calcine modified porous calcite out-phase base catalyst, for subsequent use.
2. catalyzed transesterification.Ester exchange reaction method is with embodiment mono-, and obtaining fatty acid methyl ester through gas phase analysis is 93.5%, and productive rate is 85.3%.
Embodiment tetra-,
1. the preparation of catalyst.Get 1g calcite powder in round-bottomed flask, add a certain amount of CH
3cOOH solution dissolves, stirring at room temperature adds the ethylene glycol solution of 1.98g beta-schardinger dextrin-and 10mL, with ammoniacal liquor regulation system, pH is about 7 left and right, after 25 DEG C of stirring reaction 480min, be transferred to while hot in porcelain boat ageing 60h gel in 100 DEG C of baking ovens, then in tube furnace after 830 DEG C of calcining and activating 120min, take out and put into immediately vacuum desiccator while hot, must calcine modified porous calcite out-phase base catalyst, for subsequent use.
2. catalyzed transesterification.Ester exchange reaction method is with embodiment mono-, and obtaining fatty acid methyl ester through gas phase analysis is 88.3%, and productive rate is 78.7%.
Embodiment five,
1. the preparation of catalyst.With the regenerated catalyst in embodiment mono-.
2. catalyzed transesterification.Ester exchange reaction method, with embodiment mono-, is reused after 5 times, fatty acid methyl ester 95.5%, and productive rate is 81.2%.
Embodiment six,
1. the preparation of catalyst.With the regenerated catalyst in embodiment bis-.
2. catalyzed transesterification.Ester exchange reaction method, with embodiment mono-, is reused after 5 times, and fatty acid methyl ester is 87.5%, and productive rate is 80.2%.
bibliography
[1]Liu,?X.,?He,?H.,?Wang,?Y.,?
et?al.?2008.?Fuel,?87(2):?216-221.
[2]Suppes,?G.?J.,?Bockwinkel,?K.,?Lucas,?S.?2001.?J.?Amer.?Oil.?Chem.?Soc.,?78:?139-146.
[3]Wilson,?K.,?Hardacre,?C.,?Lee,?A.?F.?2008,?Green?Chem.,?10:?654.
[4]Yoosuk,?B.,?Udomsap,?P.,?Puttasawat,?B.?2011.?Appl.?Catal.?A-Gen.,?395:?87-94.
[5]Ngamcharussrivichai,?C.,?Nunthasanti,?P.,?Tanachai,?S.?2010.?Fuel.?Process.?Technol.,?91:?1409-1415.
[6]Yoosuk,?B.,?Udomsap,?P.,?Puttasawat,?B.?2010.Chem.?Eng.?J.,?162:?135-141.
[7]Wang,?R.,?Li,?H.,?Chang,?F.?2013.?Catal.?Sci.?Technol.,?3:?2244-2251。
Claims (8)
1. the preparation method of a porous out-phase base catalyst, it is characterized in that taking richness calcium base calciferous calcite ore as raw material, generate calcium salt with acid reaction, again with monose, disaccharide, compound sugar or polysaccharide glucide or carbohydrate derivative are template, be that 1:0.5～1:10 ratio is mixed above-mentioned calcium salt and template in mass ratio, with methyl alcohol, ethanol or ethylene glycol are solvent, regulate reaction system pH as 2～7 taking organic base, at 25～150 DEG C of stirring reaction 0.5～6h, be transferred to while hot again in porcelain boat, 25～100 DEG C of ageing 24～120h gels in baking oven, finally calcining and activating 1～5h in the tube furnace of 600～850 DEG C, cooling in drier, can obtain the porous out-phase base catalyst of high specific surface area and pore volume.
2. the preparation method of a kind of porous out-phase base catalyst according to claim 1, is characterized in that described monosaccharide and disaccharide, compound sugar or polysaccharide glucide are glucose, fructose, ribose, deoxyribose, sucrose, maltose, lactose, cyclodextrin, starch, glycogen, cellulose, hemicellulose, chitin or proteoglycans; Described sugar derivatives is sugar alcohol, saccharic acid, osamine, glucosides, and described template is one or more templates that mix in glucide or carbohydrate derivative.
3. in template according to claim 2, glucide is preferably sucrose, glucose, soluble starch.
4. method according to claim 1, it is characterized in that reacting acid used is HNO
3, HCl, HCOOH or CH
3cOOH.
5. method according to claim 1, it is characterized in that reacting organic base used is ammoniacal liquor, ethylenediamine, triethylamine, pyridine.
6. method according to claim 1, is characterized in that under vacuum or condition of normal pressure calcining and activating in tube furnace, and calcination atmosphere is air stream, nitrogen stream or argon gas stream.
7. the application of porous out-phase base catalyst as claimed in claim 1, the vegetable and animals oils that to it is characterized in that for catalysis main component be fatty acid triglycercide and methyl alcohol or ethanol ester exchange reaction are prepared the catalyst of biodiesel.
8. the application of porous out-phase base catalyst according to claim 7, is characterized in that catalyst can repeatedly use, its renovation process be reacted catalyst after centrifugation, in tube furnace, 600～800 DEG C of calcining and activatings, reusable.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217791A (en) * | 2019-07-15 | 2019-09-10 | 天津工业大学 | A kind of method for preparation of active carbon based on eggshell and saccharide compound |
| EP3542897A1 (en) * | 2018-03-23 | 2019-09-25 | Omya International AG | Method for transesterification of carboxylic acid esters |
| CN110697799A (en) * | 2019-10-16 | 2020-01-17 | 河南电池研究院有限公司 | Preparation method of porous lithium ion battery anode material |
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| JP2005262126A (en) * | 2004-03-19 | 2005-09-29 | Nissan Motor Co Ltd | Catalyst carrier, its preparation method and preparation method of catalyst |
| CN101797499A (en) * | 2010-03-02 | 2010-08-11 | 浙江大学 | Preparation method of Ce-Zr-La-O compound oxide material with high specific surface |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005262126A (en) * | 2004-03-19 | 2005-09-29 | Nissan Motor Co Ltd | Catalyst carrier, its preparation method and preparation method of catalyst |
| CN101797499A (en) * | 2010-03-02 | 2010-08-11 | 浙江大学 | Preparation method of Ce-Zr-La-O compound oxide material with high specific surface |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3542897A1 (en) * | 2018-03-23 | 2019-09-25 | Omya International AG | Method for transesterification of carboxylic acid esters |
| WO2019180012A1 (en) * | 2018-03-23 | 2019-09-26 | Omya International Ag | Method for transesterification of carboxylic acid esters |
| CN111867722A (en) * | 2018-03-23 | 2020-10-30 | 欧米亚国际集团 | Method for transesterification of carboxylic acid esters |
| JP2021516676A (en) * | 2018-03-23 | 2021-07-08 | オムヤ インターナショナル アクチェンゲゼルシャフト | Methods for transesterification of carboxylic acid esters |
| JP7342013B2 (en) | 2018-03-23 | 2023-09-11 | オムヤ インターナショナル アクチェンゲゼルシャフト | Method for transesterification of carboxylic acid esters |
| CN110217791A (en) * | 2019-07-15 | 2019-09-10 | 天津工业大学 | A kind of method for preparation of active carbon based on eggshell and saccharide compound |
| CN110697799A (en) * | 2019-10-16 | 2020-01-17 | 河南电池研究院有限公司 | Preparation method of porous lithium ion battery anode material |
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