CN100400159C - Method for preparing solid acid catalyst from charing and sulfonating sugar compounds - Google Patents
Method for preparing solid acid catalyst from charing and sulfonating sugar compounds Download PDFInfo
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- CN100400159C CN100400159C CNB2006100366992A CN200610036699A CN100400159C CN 100400159 C CN100400159 C CN 100400159C CN B2006100366992 A CNB2006100366992 A CN B2006100366992A CN 200610036699 A CN200610036699 A CN 200610036699A CN 100400159 C CN100400159 C CN 100400159C
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Abstract
The present invention relates to process for charing and sulfonating saccharide compound to prepare solid acid catalyst. The process includes: charing saccharide compound material at 300-500deg.c under N2 protection for 10-30 hr; the subsequent sulfonating with concentrated sulfuric acid at 100-250deg.c for 10-30 hr to obtain a mixture; adding water through stirring, standing, precipitating, filtering and drying to obtain solid acid catalyst. The solid acid catalyst can catalyze the esterification of higher fatty acid and short chain alcohol and can reach esterification converting rate up to 95 % in 4-10 hr. The preparation process is simple and has facile materials, and the prepared catalyst has high catalytic activity, environment friendship, easy recovering and high stability, and may be used widely in esterification, hydrolysis, alkylation and other organic reactions.
Description
Technical field
The present invention relates to a kind of preparation method of solid acid catalyst, particularly a kind of charing and sulfonating sugar compounds prepare the method for solid acid catalyst.
Background technology
Liquid acid catalyst such as sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid are widely used in many organic reactions such as catalytic esterification, hydrolysis, alkylation, aquation and Beckmann rearrangement, yet, liquid acid catalysis has following problems: (1) has corrosiveness to equipment, and equipment must adopt expensive resistant material or carry out anti-corrosion treatment; (2) liquid acid catalyst is difficult to separate with reactant mixture; (3) liquid acid catalytic process accessory substance is many, and product need decolour; (4) catalyst is difficult to utilize again, produces a large amount of acid waste liquids that contains.
The appearance of solid acid catalyst has changed the homogeneous reaction process of traditional liquid acid catalyst, make heterogeneousization of homogeneous reaction, this has just overcome the shortcoming that catalyst and raw material and product are difficult to separate, and solid acid catalyst does not exist the severe corrosive and the toxicity of traditional liquid acid catalyst, also having reduced discharging wastes, is real environment-friendly catalyst.But the preparation method of existing solid acid catalyst exists also that preparation cost higher (particularly like this when being carrier with the oxide of rare metal Ti, Zr), complicated process of preparation, reaction temperature are higher, the easy inactivation of catalyst and catalyst regeneration difficulty, easily make the shortcoming of product painted (especially iron content solid acid).
Summary of the invention
The objective of the invention is to deficiency at existing acid catalyst, the method that a kind of charing and sulfonating sugar compounds prepare solid acid catalyst is proposed, with the saccharide compound is raw material, through charing, sulfonation and prepare a kind of high activity, with low cost, good stability, reusable solid acid catalyst.
The method that charing of the present invention and sulfonating sugar compounds prepare solid acid catalyst comprises: with the raw material saccharide compound under nitrogen protection, in 300～500 ℃ of charing 10～30h, add the concentrated sulfuric acid then, obtain mixture at 100～250 ℃ of sulfonation 10～30h, add in mixture that entry is stirred, leaves standstill, precipitated, filtration, drying can make solid acid catalyst; The described concentrated sulfuric acid is 10～30: 1 with the ratio of the quality of saccharide compound consumption.
Described saccharide compound is one or more the above mixtures in monose, disaccharides, the polysaccharide; Described monose is D-glucose, and described disaccharides is a sucrose, and described polysaccharide is cellulose and/or starch.
The solid acid catalyst of the inventive method preparation is based on saccharide compound, and load has sulfonic group.It is raw material that its preparation method has adopted saccharide compound cheap and easy to get, through with the incomplete charing of raw material, forms an extremely stable carrier with many cyclophanes carbon structure, and sulfonation forms the catalytic active center of solid acid then.The activity of described catalyst higher fatty acids and short chain alcohol esterification is higher than traditional solid acid (niobic acid, high fluoride resin etc.) far away, and highly stable; Filter and to recycle and reuse by simple decant.Therefore, can be widely used in many organic reactions such as catalytic esterification, hydrolysis, alkylation, aquation and Beckmann rearrangement.
The present invention has following advantage compared with prior art:
(1) adopting saccharide compound cheap and easy to get is raw material, has reduced production cost, has overcome the rare shortcoming of conventional solid acid vectors material expensive;
(2) the solid acid catalyst catalysis LCFA of the inventive method preparation and short chain fatty alcohol esterification condition are gentle, course of reaction is simple and easy to control, and having overcome the conventional solid acid catalyst needs the shortcoming of reaction at high temperature;
(3) the solid acid catalyst good stability of the inventive method preparation, and filter and can recycle and reuse by simple decant has overcome conventional solid acid catalyst shortcoming of inactivation and catalyst regeneration difficulty easily in reaction.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is described in further detail, the present invention is not limited to this.
Embodiment 1
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 15h; The gained powder uses the 50mL concentrated sulfuric acid (＞96%) in 100 ℃ of sulfonation 10h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 95%.
Embodiment 2
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 300 ℃ of charing 15h; The gained powder uses the 60mL concentrated sulfuric acid (＞96%) in 100 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.76g after 5 hours, the methyl oleate yield is 93%.
Embodiment 3
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 500 ℃ of charing 15h; The gained powder uses the 70mL concentrated sulfuric acid (＞96%) in 100 ℃ of sulfonation 30h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 94%.
Embodiment 4
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 10h; The gained powder uses the 80mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 10h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 700mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.56g palmitic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl hexadecanoate 2.57g after 5 hours, the methyl hexadecanoate yield is 95%.
Embodiment 5
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 30h; The gained powder uses the 90mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 700mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.85g stearic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl stearate 2.84g after 5 hours, the methyl stearate yield is 95%.
Embodiment 6
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 15h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 30h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 700mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.28g myristic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get myristic acid methyl esters 2.28g after 5 hours, myristic acid methyl esters yield is 94%.
Embodiment 7
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 500 ℃ of charing 15h; The gained powder uses the 110mL concentrated sulfuric acid (＞96%) in 250 ℃ of sulfonation 10h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 300mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.00g laurate and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl laurate 2.04g after 5 hours, the methyl laurate yield is 95%.
Embodiment 8
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 500 ℃ of charing 10h; The gained powder uses the 120mL concentrated sulfuric acid (＞96%) in 250 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 300mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 3.13g arachidic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl arachidate 3.07g after 5 hours, the methyl arachidate yield is 94%.
Embodiment 9
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 500 ℃ of charing 30h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 250 ℃ of sulfonation 30h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl oleate 2.92g after 7 hours, the ethyl oleate yield is 94%.
Embodiment 10
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 350 ℃ of charing 15h; The gained powder uses the 130mL concentrated sulfuric acid (＞96%) in 125 ℃ of sulfonation 10h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 300mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, the acid of 2.56g palmitic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl palmitate 2.70g after 7 hours, the ethyl palmitate yield is 95%.
Embodiment 11
Take by weighing 10g D-glucose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 375 ℃ of charing 15h; The gained powder uses the 140mL concentrated sulfuric acid (＞96%) in 175 ℃ of sulfonation 20h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, 2.85g stearic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl stearte 2.92g after 7 hours, the ethyl stearte yield is 94%.
Embodiment 12
Take by weighing 10g sucrose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 425 ℃ of charing 15h; The gained powder uses the 150mL concentrated sulfuric acid (＞96%) in 225 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 95%.
Embodiment 13
Take by weighing the 10g cellulose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 450 ℃ of charing 15h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 18h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl oleate 2.92g after 7 hours, the ethyl oleate yield is 94%.
Embodiment 14
Take by weighing 10g starch, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 475 ℃ of charing 10h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 22h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 95%.
Embodiment 15
Take by weighing the mixture of 10g D-dextrose plus saccharose, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 18h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 28h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 95%.
Embodiment 16
Take by weighing the mixture of 10g D-grape sugar and starch, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 25h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl oleate 2.92g after 7 hours, the ethyl oleate yield is 94%.
Embodiment 17
Take by weighing 10g sucrose and cellulosic mixture, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 28h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 3.20g methyl alcohol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get methyl oleate 2.82g after 5 hours, the methyl oleate yield is 95%.
Embodiment 18
Take by weighing the mixture of 10g D-glucose, sucrose and starch, under nitrogen protection,, obtain the pitchy solid, cooling back pulverize in 400 ℃ of charing 15h; The gained powder uses the 100mL concentrated sulfuric acid (＞96%) in 150 ℃ of sulfonation 15h under nitrogen protection then, is cooled to room temperature; Mixture is joined in the 500mL distilled water, stir, leave standstill, the precipitation of solid material of black gets off, and cleans repeatedly until washing lotion with boiling water to be neutral again, obtains solid acid catalyst after the drying.
Effect: the 4.60g ethanol of in round-bottomed flask, packing into, 2.82g oleic acid and 0.14g solid acid catalyst, in 80 ℃ of backflows, get ethyl oleate 2.92g after 7 hours, the ethyl oleate yield is 94%.
Under the identical reaction condition, the catalyst (embodiment 1) and solid super-strong acid SO of the inventive method preparation
4 2-/ TiO
2The contrast situation as shown in table 1:
Table 1
| Catalyst | Sintetics | Productive rate | Stability |
| The solid acid catalyst of embodiment 1 | Methyl oleate | 95％ | Promptly reusable after simple the recovery |
| Solid super-strong acid SO 4 2-/TiO 2 | Methyl oleate | 90％ | The high-temperature activation rear is reusable |
Last table explanation, under the same terms, the catalyst higher fatty acids of the inventive method preparation and the productive rate of short chain alcohol esterification are higher than solid super-strong acid SO
4 2-/ TiO
2Therefore, its catalytic effect and reactivity excellence are in solid super-strong acid.By contrast, its stability is better than solid super-strong acid SO far away
4 2-/ TiO
2
Claims (5)
1. charing and sulfonating sugar compounds prepare the method for solid acid catalyst, it is characterized in that: with the raw material saccharide compound under nitrogen protection, in 300～500 ℃ of charing 10～30h, add the concentrated sulfuric acid then, obtain mixture at 100～250 ℃ of sulfonation 10～30h, add in mixture that entry is stirred, leaves standstill, precipitated, filtration, drying can make solid acid catalyst; The described concentrated sulfuric acid and saccharide compound amount ratio are 10～30: 1 quality.
2. method according to claim 1 is characterized in that described saccharide compound is one or more the above mixtures in monose, disaccharides, the polysaccharide.
3. method according to claim 2 is characterized in that described monose is D-glucose.
4. method according to claim 2 is characterized in that described disaccharides is a sucrose.
5. method according to claim 2 is characterized in that described polysaccharide is cellulose and/or starch.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485997B (en) * | 2009-02-12 | 2011-03-30 | 华东理工大学 | Method for preparing carboneous solid acid catalyst |
| CN101691526B (en) * | 2009-09-30 | 2012-11-28 | 华中农业大学 | Method for preparing biodiesel by using biological carapace solid base catalyst |
| CN101890364B (en) * | 2010-06-25 | 2012-06-27 | 西北农林科技大学 | Method of using agricultural and forestry waste to prepare solid-acid catalyst |
| CN102125874A (en) * | 2011-01-07 | 2011-07-20 | 华南理工大学 | Method for preparing carbon based solid acid catalyst by using waste biomass as raw material |
| CN102247888A (en) * | 2011-05-19 | 2011-11-23 | 北京化工大学 | Preparation method for granular carbon-based solid acid catalyst for producing biological diesel oil |
| CN102504028A (en) * | 2011-10-11 | 2012-06-20 | 常茂生物化学工程股份有限公司 | Method for preparing organic cellulose acid ester by solid acid catalysts |
| CN103084188B (en) * | 2012-12-20 | 2015-03-11 | 华南理工大学 | Solid acid catalyst containing catalytic active group and adsorption group and preparation and application of solid acid catalyst |
| CN104028294B (en) * | 2014-06-26 | 2016-02-03 | 江南大学 | A kind of solid acid catalyst and preparation method thereof being suitable for microwave radiation technology reaction |
| CN105498801A (en) * | 2015-12-29 | 2016-04-20 | 华南理工大学 | Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst |
| CN106268940A (en) * | 2016-08-10 | 2017-01-04 | 华南理工大学 | Xylan base carbon-based solid acid and the method being catalyzed and synthesized benzodiphenylene oxide compounds by it |
| CN109046381B (en) * | 2018-06-02 | 2021-06-01 | 太原理工大学 | Sulfur-carbon based solid acid catalyst |
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Application publication date: 20070124 Assignee: Shenzhen Xin Bao eco-friendly power source Science and Technology Ltd. Assignor: South China University of Technology Contract record no.: 2013440000310 Denomination of invention: Method for preparing solid acid catalyst from charing and sulfonating sugar compounds Granted publication date: 20080709 License type: Exclusive License Record date: 20130609 |
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