CN102078823B - Carbon-based solid acid catalyst and preparation method thereof - Google Patents
Carbon-based solid acid catalyst and preparation method thereof Download PDFInfo
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- CN102078823B CN102078823B CN 201010566959 CN201010566959A CN102078823B CN 102078823 B CN102078823 B CN 102078823B CN 201010566959 CN201010566959 CN 201010566959 CN 201010566959 A CN201010566959 A CN 201010566959A CN 102078823 B CN102078823 B CN 102078823B
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Abstract
The invention provides a carbon-based solid acid catalyst and a preparation method thereof. The method comprises the following steps of: 1) putting a metal oxide into organic matter aqueous solution for soaking, drying by distillation and carbonizing so as to obtain a carbon/oxide compound; 2) performing a sulfonation reaction on the carbon/oxide compound so as to obtain a sulfonated carbon/oxide compound; and 3) reacting the sulfonated carbon/oxide compound with acid or alkali so as to obtain the carbon-based solid acid catalyst. The carbon-based solid acid catalyst prepared by the method has high dispersibility and hydrophobicity in a liquid phase reaction system and high catalytic activity in an esterification reaction of oleic acid and methanol.
Description
Technical field
The present invention relates to a kind of carbon-based solid acid catalyst and preparation method thereof, belong to the solid catalyst field.
Background technology
Carbon-based solid acid catalyst has chemical inertness, surface hydrophobic, good mechanical stability and heat endurance, is a kind of ideal catalyst that is applied to liquid-phase reaction system.
Carbon-based solid acid catalyst is the earliest by propositions (Nature, 438,178) such as Japanese scholars Hara.They use concentrated acid sulfonation again with the direct high temperature cabonization of the saccharide compounds such as sucrose, thereby obtain with sulfonic amorphous carbon catalyst.This catalyst has good catalytic activity in the liquid phase reactors such as esterification, in the esterification of the LCFA that particularly relates in the biodiesel preparation, carbon-based solid acid shows than conventional solid acid Nafion and the higher catalytic activity of Amberlyst-15.
Chinese patent (publication number: CN1899691 A) announced a kind of preparation method of carbon-based solid acid, namely obtained catalyst by direct carbonization and concentrated acid sulfonation saccharide compound.Also have in addition patent of invention (publication number: CN101314138 A) adopt living beings as raw material to reduce preparation cost.Said method all is the direct carbonization raw material, and the catalyst granules that makes is large, and dispersiveness is not good in liquid-phase reaction system, is unfavorable for fully contacting of reactant and catalytic active center.Therefore, be necessary to provide a kind of granularity solid acid catalyst little, that good dispersion and catalytic activity are high in system and preparation method thereof.
Summary of the invention
The purpose of this invention is to provide a kind of carbon-based solid acid catalyst that is easy in liquid-phase reaction system, disperse and preparation method thereof.
The preparation method of carbon-based solid acid catalyst provided by the invention comprises the steps:
1) metal oxide is placed carries out carbonization behind organic aqueous solution dipping and the evaporate to dryness and obtain carbon/complex oxide;
2) described carbon/complex oxide is carried out sulfonating reaction and obtain sulfonation carbon/complex oxide;
3) described sulfonation carbon/complex oxide and acid or alkali reaction are namely got described carbon-based solid acid catalyst.
Among the above-mentioned preparation method, step 1) described metal oxide can be Al
2O
3, SiO
2And TiO
2In at least a; The particle diameter of described metal oxide and aperture can be respectively 2nm-100nm and 5nm-15nm.
Among the above-mentioned preparation method, step 1) organic matter in the described organic aqueous solution can be sucrose or starch; The quality percentage composition that described organic matter accounts for described organic aqueous solution can be 35%-40%, such as 37.5%.
Among the above-mentioned preparation method, step 1) time of described dipping can be 30 minutes-50 minutes, such as 30 minutes or 45 minutes; Described evaporate to dryness carries out under water-bath; The temperature of described water-bath is 75 ℃-85 ℃, such as 80 ℃.
Among the above-mentioned preparation method, step 1) described carbonization is carried out under inert gas, such as nitrogen; The temperature of described carbonization is 500 ℃-800 ℃, such as 500 ℃, 600 ℃ or 800 ℃; The time of described carbonization was 0.5 hour-1 hour, such as 0.5 hour or 1 hour.
Among the above-mentioned preparation method, step 2) sulfonating agent of described sulfonating reaction is the benzene sulfonic acid diazol; The ratio of quality and the number of copies of carbon/complex oxide and sulfonating agent is (18-31) in the described sulfonating reaction: 1, such as 31: 1 or 17: 1; The temperature of described sulfonating reaction is 0 ℃～5 ℃, such as 0 ℃, 3 ℃ or 5 ℃; The time of described sulfonating reaction was 2 hours-8 hours, such as 3 hours; The solvent of described sulfonating reaction is water.
Among the above-mentioned preparation method, described benzene sulfonic acid diazol can be prepared by diazo-reaction by sulfanilic acid.
Among the above-mentioned preparation method, step 2) also comprise described sulfonation carbon/complex oxide is filtered, washs and dry step; The solvent of described washing is followed successively by water, DMF and acetone; The temperature of described drying is 100 ℃-120 ℃, such as 110 ℃; The time of described drying is 6 hours-9 hours.
Among the above-mentioned preparation method, step 3) described acid can be hydrofluoric acid, and described alkali can be NaOH; Described sulfonation carbon/complex oxide can be 1 with the ratio of quality and the number of copies of acid: (5-10), and such as 1: 7 or 1: 10; The ratio of quality and the number of copies of described sulfonation carbon/complex oxide and alkali can be 7: 4; The time of described reaction can be 2 hours-4 hours, such as 3 hours; Described reaction also comprises filters described carbon-based solid acid catalyst, wash and dry step; The temperature of described drying is 100 ℃-120 ℃, such as 110 ℃; The time of described drying was 6 hours-9 hours, such as 8 hours.
Among the above-mentioned preparation method, step 1) also comprise one or many place described organic aqueous solution to flood described carbon/complex oxide and evaporate to dryness after the step of carbonization.Can obtain the different carbon/complex oxide of phosphorus content by carrying out the one or many above-mentioned steps, in order to prepare the different carbon-based solid acid catalyst of granularity.
The present invention also provides the carbon-based solid acid catalyst by the said method preparation, and sulfonic content is 1.4mmol/g-1.7mmol/g in the described carbon-based solid acid catalyst, such as 1.41mmol/g, 1.5mmol/g or 1.7mmol/g.
The preparation method of carbon-based solid acid catalyst provided by the invention all adopts raw material cheap and easy to get; Carbon-based solid acid catalyst by the method preparation has following advantage: 1) good dispersion, the dynamic laser scattering analysis shows, the carbon-based solid acid catalyst that the present invention makes can partly be dispersed into particle diameter tens to the granule of hundreds of nanometer in the Liquid Phase Methanol reaction system.The transmission electron microscope photo demonstration, the granule that is dispersed into has the structure of thin-walled porous.Compare with the sulfonation active carbon, catalyst of the present invention has better dispersiveness in methyl alcohol, is conducive to contacting of reactant and catalytic active center.Therefore, although active sites density is close with the sulfonation active carbon, catalyst of the present invention demonstrates higher activity in the esterification of oleic acid and methyl alcohol.2) catalytic activity is high, Amberlyst-15 compares with the conventional solid acid catalyst, the active sites density of catalyst of the present invention only has 1/3rd of Amberlyst-15, but in the esterification of oleic acid and methyl alcohol, reactant transformation frequency (TOF) is seven times of Amberlyst-15.This is not only because catalyst of the present invention has good dispersiveness, and also because of carbon-based solid acid and resin-phase ratio, surface hydrophobic is stronger, more is conducive to the water of esterification generation from the catalyst surface desorption, thereby improves reaction rate.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the carbon-based solid acid of the embodiment of the invention 1 preparation.
Fig. 2 is the following particle diameter distribution map of dynamic light scattering 1 μ m of the carbon-based solid acid of the embodiment of the invention 1 preparation.
The specific embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Used active carbon is available from Beijing Fine Chemical Works energetically in the following Comparative Examples of the present invention; Used sulfonic group ion exchange resin Amberlyst-15 is available from Acros Organics company.
The particle diameter of used silica, aluminium oxide and titanium oxide is 2nm-100nm among the following embodiment of the present invention; The aperture is 5nm-15nm.
The preparation of embodiment 1, carbon-based solid acid catalyst and the catalytic effect in catalytic esterification thereof
1) the 9g aluminium oxide is placed the aqueous sucrose solution (the quality percentage composition of sucrose is 37.5%) that contains 2.7g sucrose, left standstill after the stirring 45 minutes, evaporate to dryness obtains pressed powder under 80 ℃ of water-baths.The gained pressed powder is carried out carbonization 1 hour under under the nitrogen protection 600 ℃, obtain the black solid powder and be carbon/alumina compound 9.3g;
2) get the 0.22g sulfanilic acid, make its dissolving with 4ml hydrochloric acid (1mol/L) and 30ml deionized water, and place 0 ℃ of ice-water bath, add again the 88mg natrium nitrosum, leave standstill after the stirring and it was fully reacted in 15 minutes, obtain containing the settled solution of 0.22g benzene sulfonic acid diazol;
Get step 1) black solid powder 6.7g, add the 40ml deionized water, place 0 ℃ of ice-water bath; Add above-mentioned settled solution (wherein under the electromagnetic agitation, the mass ratio of carbon/alumina compound and benzene sulfonic acid diazol is 31: 1), continue stirring reaction after 3 hours, filter, the gained black powder is used deionized water, N successively, then dinethylformamide and acetone washing namely got sulfonation carbon/alumina compound 6.9g in 8 hours in 110 ℃ of lower oven dry;
3) with step 2) sulfonation carbon/alumina compound 6.9g and 50ml hydrofluoric acid (mass ratio of sulfonation carbon/alumina compound and hydrofluoric acid is 1: 7) mix and blend 3 hours, again filter, extremely neutral with the deionized water washing, namely got carbon-based solid acid catalyst in 8 hours in 110 ℃ of oven dry, wherein, sulfonic content is 1.41mmol/g.
Get above-mentioned solid acid 50mg, add in the 20ml hydrothermal reaction kettle with 8ml absolute methanol and 1g oleic acid, reaction is 2 hours under 77 ℃ of water-bath electromagnetic agitation, obtains methyl oleate, and the productive rate that gets methyl oleate is 91%.System to above-mentioned esterification is carried out the laser light scattering analysis, and Fig. 2 is the following particle diameter distribution map of dynamic light scattering 1 μ m of the carbon-based solid acid of the present embodiment preparation.Analyzed as can be known by this, the hydrodynamic radius of this carbon-based solid acid mainly is distributed between the 57nm-1149nm, and mean radius is 265nm.System to above-mentioned esterification is carried out transmission electron microscope analysis, and Fig. 1 is the transmission electron microscope photo of the carbon-based solid acid of the present embodiment preparation, and this photo shows that this carbon-based solid acid has the granule of thin-walled loose structure.
The preparation of embodiment 2, carbon-based solid acid catalyst and the catalytic effect in catalytic esterification thereof
1) the 6g titanium oxide is placed the aqueous sucrose solution (the quality percentage composition of sucrose is 37.5%) that contains 1.8g sucrose, left standstill after the stirring 45 minutes, evaporate to dryness obtains pressed powder under 80 ℃ of water-baths.The gained pressed powder is carried out carbonization 0.5 hour under under the nitrogen protection 500 ℃, obtain the black solid powder and be carbon/titanium oxide compound 6.2g;
Gained 3g carbon/titanium oxide compound is placed the aqueous sucrose solution (the quality percentage composition of sucrose is 37.5%) that contains 0.9g sucrose again, left standstill after the stirring 45 minutes, evaporate to dryness obtains pressed powder under 80 ℃ of water-baths.The gained pressed powder is carried out carbonization 0.5 hour under under the nitrogen protection 500 ℃, obtain the black solid powder and be carbon/titanium oxide compound 3.1g;
2) get step 1) black solid powder 3.7g, add the 40ml deionized water, place 5 ℃ of ice-water baths; Add the settled solution (preparation of benzene sulfonic acid diazol is with step 2 among the embodiment 1) that contains 0.22g benzene sulfonic acid diazol under the electromagnetic agitation, wherein, the mass ratio of carbon/alumina compound and benzene sulfonic acid diazol is 17: 1), continue stirring reaction after 3 hours, filter, then the gained black powder namely got sulfonation carbon/titanium oxide compound 3.9g in 8 hours in 110 ℃ of lower oven dry successively with deionized water, DMF and acetone washing;
3) with step 2) sulfonation carbon/titanium oxide compound 3.9g and 40ml hydrofluoric acid (mass ratio of hydrofluoric acid and sulfonation carbon/titanium oxide compound is 10: 1) mix and blend 3 hours, again filter, extremely neutral with the deionized water washing, namely got carbon-based solid acid catalyst in 8 hours in 110 ℃ of oven dry, wherein, sulfonic content is 1.7mmol/g.
Get above-mentioned solid acid 50mg, add in the 20ml hydrothermal reaction kettle with 8ml absolute methanol and 1g oleic acid, reaction is 4.5 hours under 77 ℃ of water-bath electromagnetic agitation, obtains methyl oleate, and the productive rate of methyl oleate is 97%.
The preparation of embodiment 3, carbon-based solid acid catalyst and the catalytic effect in catalytic esterification thereof
1) 9g silica is placed the aqueous sucrose solution (the quality percentage composition of sucrose is 37.5%) that contains 2.7g sucrose, left standstill after the stirring 30 minutes, evaporate to dryness obtains pressed powder under 80 ℃ of water-baths.The gained pressed powder is carried out carbonization 0.5 hour under under the nitrogen protection 800 ℃, obtain the black solid powder and be carbon/silica compound 9.3g;
2) get step 1) black solid powder 6.7g, add the 40ml deionized water, place 3 ℃ of ice-water baths; Add under the electromagnetic agitation contain 0.22g benzene sulfonic acid diazol settled solution (preparation method of benzene sulfonic acid diazol is with step 2 among the embodiment 1) wherein the mass ratio of carbon/alumina compound and benzene sulfonic acid diazol be 31: 1), continue stirring reaction after 3 hours, filter, the gained black powder is used deionized water, N successively, then dinethylformamide and acetone washing namely got sulfonation carbon/silica compound 6.9g in 6 hours in 110 ℃ of lower oven dry;
3) with step 2) sulfonation carbon/silica compound 6.9g and the 50ml NaOH aqueous solution (2mol/L) (mass ratio of NaOH and sulfonation carbon/titanium oxide compound is 4: 7), mix and blend 3 hours, again filter, extremely neutral with the deionized water washing, namely got carbon-based solid acid catalyst in 8 hours in 110 ℃ of oven dry, wherein, sulfonic content is 1.5mmol/g.
Get above-mentioned solid acid 50mg, add in the 20ml hydrothermal reaction kettle with 8ml absolute methanol and 1g oleic acid, reaction is 3 hours under 77 ℃ of water-bath electromagnetic agitation, obtains methyl oleate, and the productive rate of methyl oleate is 91%.
The preparation of Comparative Examples 1, sulfonation activated carbon and the catalytic effect in catalytic esterification thereof
1) gets the 0.22g sulfanilate, make its dissolving with 4ml hydrochloric acid (1mol/L) and 30ml deionized water, and place 5 ℃ of ice-water baths, add again the 88mg natrium nitrosum, leave standstill after the stirring and it was fully reacted in 15 minutes, obtain the settled solution of benzene sulfonic acid diazol;
2) get active carbon powder 0.54g, add the 40ml deionized water, place 5 ℃ of ice-water baths.Adding step 1 under the electromagnetic agitation) settled solution continued stirring reaction after 3 hours, filtered, and the gained black powder with deionized water, DMF and acetone washing, in 110 ℃ of oven dry, namely gets the sulfonation activated carbon successively.
Get above-mentioned solid acid 50mg, add in the 20ml hydrothermal reaction kettle with 8ml absolute methanol and 1g oleic acid, reaction is 6 hours under 77 ℃ of water-bath electromagnetic agitation, obtains methyl oleate, and the productive rate that records methyl oleate is 92%.
Comparative Examples 2, the catalytic effect of sulfonic group ion exchange resin in catalytic esterification
Get sulfonic group ion exchange resin Amberlyst-15 50mg, add in the 20ml hydrothermal reaction kettle with 8ml absolute methanol and 1g oleic acid, reaction is 6 hours under 77 ℃ of water-bath electromagnetic agitation, obtains methyl oleate, and the productive rate that records methyl oleate is 75%.
Claims (2)
1. the preparation method of a carbon-based solid acid catalyst comprises the steps:
1) the 9g aluminium oxide is placed the aqueous sucrose solution that contains 2.7g sucrose, the quality percentage composition of sucrose in described aqueous sucrose solution is 37.5%, leaves standstill after the stirring 45 minutes, and evaporate to dryness obtains pressed powder under 80 ℃ of water-baths; The gained pressed powder is carried out carbonization 1 hour under under the nitrogen protection 600 ℃, obtain the black solid powder and be carbon/alumina compound 9.3g;
2) get the 0.22g sulfanilic acid, 4ml hydrochloric acid and 30ml deionized water with 1mol/L make its dissolving, and place 0 ℃ of ice-water bath, add the 88mg natrium nitrosum again, leave standstill after the stirring and it was fully reacted in 15 minutes, obtain containing the settled solution of 0.22g benzene sulfonic acid diazol;
Get the black solid powder 6.7g of step 1), add the 40ml deionized water, place 0 ℃ of ice-water bath; Add above-mentioned settled solution under the electromagnetic agitation, the mass ratio of carbon/alumina compound and benzene sulfonic acid diazol is 31:1, continue stirring reaction after 3 hours, filter, the gained black powder is used deionized water, N successively, then dinethylformamide and acetone washing namely got sulfonation carbon/alumina compound 6.9g in 8 hours in 110 ℃ of lower oven dry;
3) with step 2) sulfonation carbon/alumina compound 6.9g and 50ml hydrofluoric acid, the mass ratio of sulfonation carbon/alumina compound and hydrofluoric acid is 1:7, mix and blend 3 hours, again filter, extremely neutral with the deionized water washing, namely got carbon-based solid acid catalyst in 8 hours in 110 ℃ of oven dry, wherein, sulfonic content is 1.41mmol/g.
2. the carbon-based solid acid catalyst of the described method of claim 1 preparation, sulfonic content is 1.41mmol/g in the described carbon-based solid acid catalyst.
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| CN102614917B (en) * | 2012-03-02 | 2013-10-30 | 宁夏大学 | Preparation method of composite carbon base solid acid catalyst |
| CN103071476A (en) * | 2013-01-24 | 2013-05-01 | 中国科学院青岛生物能源与过程研究所 | Preparation method of Ti hybrid carbon-based solid acid catalyst |
| CN103691454B (en) * | 2013-12-24 | 2016-10-05 | 天津大学 | A kind of preparation method and applications of mesoporous carbon based solid acid catalyst |
| CN109513449B (en) * | 2018-11-22 | 2024-05-07 | 南京林业大学 | Method for preparing solid super acid from metal organic framework material UiO-66, product and application thereof |
| CN110156014B (en) * | 2019-05-28 | 2020-10-23 | 南昌大学 | Method for preparing hydrophobic strong acid carbon material based on alkylation reaction and hydrophobic strong acid carbon material |
| CN112705247B (en) * | 2019-10-24 | 2022-12-09 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method and application thereof |
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| CN113493529B (en) * | 2020-04-07 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex with double particle size distribution |
| CN111659420A (en) * | 2020-06-08 | 2020-09-15 | 太原理工大学 | Preparation method of sulfur-carbon-based solid acid catalyst |
| CN114570388A (en) * | 2020-12-01 | 2022-06-03 | 中国石油天然气股份有限公司 | Preparation method of diesel functional component, catalyst for preparing diesel component and application of catalyst |
| CN112973740B (en) * | 2021-02-25 | 2022-07-01 | 南昌大学 | Biochar-based core-shell solid acid catalyst and preparation and application thereof |
| CN114558559B (en) * | 2022-02-21 | 2023-04-28 | 西安交通大学 | Carbon sphere-oxide composite catalytic material and preparation method and application thereof |
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