CN103071476A - Preparation method of Ti hybrid carbon-based solid acid catalyst - Google Patents
Preparation method of Ti hybrid carbon-based solid acid catalyst Download PDFInfo
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- CN103071476A CN103071476A CN2013100284846A CN201310028484A CN103071476A CN 103071476 A CN103071476 A CN 103071476A CN 2013100284846 A CN2013100284846 A CN 2013100284846A CN 201310028484 A CN201310028484 A CN 201310028484A CN 103071476 A CN103071476 A CN 103071476A
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Abstract
The invention provides a preparation method of a Ti/C hybrid carbon-based solid acid catalyst. The method comprises the following steps of 1), mixing and heating absorbent cotton and a titanium-containing precursor at a certain mass ratio, 2), carbonizing, 3), sulphonating, and 4) washing to no SO4<2->. Raw materials adopted in the preparation method are cheap; the prepared catalyst is high in catalytic activity; the catalyst is easy to recycle after catalytic hydrolysis; a product is automatically separated from the catalyst; extraction is easy; reaction conditions are mild; and an industrial application is easy to realize.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to particularly a kind of Ti of containing hydridization carbon back (Ti/C) solid acid catalyst and preparation method thereof.
Background technology
Current, inorganic acid is widely used in the industrialization such as esterification, isomerization, hydrolysis reactions, although they have than the highland catalytic activity, has serious corrosivity, toxicity, is difficult to the problem such as separating-purifying.Develop a kind of course of reaction green non-pollution, be easy to reclaim, and have highly active catalyst and become a kind of trend.It is acid strong that solid acid has, and avirulence is active high, and easily reclaim, the advantage such as capable of circulation and cause that day by day people pay close attention to.The carbon-based solid acid preparation is simple, with low cost, and a large amount of sulfonic groups, carboxyl and phenolic hydroxyl group functional group are arranged and have the acidity of working as with sulfuric acid phase at surperficial anchor chain, be a kind of desirable solid acid catalyst.
At present, there is large quantity research report carbon-based solid acid to be widely used in the hydrolysis of alkylated reaction, living beings and the synthetic aspect of biodiesel.Zhou Lina etc. (Zhou Lina, Liu can, Hua Weiming etc. the preparation of the sulfonated solid-acid material of carbon back and catalytic performance thereof [J]. the catalysis journal, 2009,30 (3): the carbon-based solid acid as catalyst, the dimethylbenzene that 196-200) make with sucrose are made solvent, the alkylated reaction optimum process condition of hydroquinones and the tert-butyl alcohol is: 150 ℃, the reaction 4h, the 2-TBHQ selectively be 78%.(the Wu Rina such as Wu Rina, Wang Tonghua, repair the will dragon, Deng. the preparation of biomass carbon based solid acid catalyst [J]. the catalysis journal, 2009,30 (12): 1203-1208) esterification of the standby biodiesel of biomass carbon based solid acid catalysis oleic acid and Methanol is studied, and inquired into the preparation technology of carbon-based solid acid to the impact of esterification, high energy makes the conversion ratio of oleic acid reach 96.1%.(the Yang Xiaomin such as Yang Xiaomin, Wan Jinquan. the research [J] of the preparation of sulfonation carbon solid acid catalyst and catalytic performance thereof. modern chemical industry, 2011,31 (10): 3437) hydrolysis reactivity of carbon-based solid acid catalyst to microcrystalline cellulose is studied, the result shows, 180 ℃ of reaction temperatures, reaction time 6h, catalyst amount 0.15g are optimum reaction condition, and the highest sugar yield is 68.71%.
Yet still there is little, the active low problem of specific area in carbon-based solid acid.At present, carbon source for the preparation of carbon back adopts biomass sugar compounds cheap and easy to get mostly, but the specific surface area of catalyst of gained is difficult to improve, thus on this basis, develop a kind of specific area higher, more efficiently the carbon-based solid acid catalyst system and catalyzing address these problems particularly important.
Summary of the invention
The object of the invention is to provide a kind of preparation method of Ti/C hydridization carbon-based solid acid catalyst, said method comprising the steps of:
5) in organic solvent with absorbent cotton and titaniferous presoma in mass ratio 5:2-20 mix, then in 150 ℃ to 250 ℃ temperature range, heat, reacted 0.5 to 24 hour;
6) with the at a certain temperature carbonization of mixture that obtains in the step 1);
7) to step 2) in add sulfonating agent in the product that obtains and carry out sulfonation; With
8) washing step 3) in the product that obtains to without SO
4 2-
Wherein used organic solvent comprises and is selected from methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol n-butanol and the isobutanol one or more in the step 1), is preferably methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, more preferably ethanol; The mass ratio of absorbent cotton and titaniferous presoma is preferably 5:2-15, and more preferably 5:2-10 most preferably is 5:8.If the mass ratio range of absorbent cotton and titaniferous presoma is lower than 5:2, then TiO
2Incomplete in the degreasing cotton fiber surface coverage; If the mass ratio range of absorbent cotton and titaniferous presoma is higher than 5:20, then can the titaniferous presoma excessive, cause cost to improve.
Described titaniferous presoma is to be selected from tetraethyl titanate, butyl titanate, isopropyl titanate and the metatitanic acid monooctyl ester one or more, is preferably tetraethyl titanate, butyl titanate, isopropyl titanate; More preferably butyl titanate and isopropyl titanate.
Reaction temperature is preferably 160 ℃ to 200 ℃ scope, more preferably 180 ℃; Reaction is preferably 1 to 20 hour, more preferably 5 to 15 hours, most preferably is 12 hours.
Step 2) carburizing temperature is 400 ℃ to 700 ℃ in, is preferably 400 ℃ to 650 ℃, and more preferably carbonization time is 0.5 to 4 hour.In carburizing temperature scope of the present invention, raise with carburizing temperature, the Ti load of the Ti/C hybrid material that then obtains is more firm, the Ti/SO that obtains after sulfonation
4The superpower solid acid ratio of type is higher.
The sulfonating agent that adopts in the step 3) is selected from a kind of in 98% concentrated sulfuric acid, 20% oleum or 50% oleum, and sulfonation temperature is 60 ℃ to 160 ℃, is preferably 120 ℃ to 140 ℃, and the sulfonation time is 4 to 16 hours, is preferably 8 to 12 hours.If sulfonation temperature is crossed low or the sulfonation time is too short, then can cause the sulfonation degree of catalyst inadequate, acidity is not strong; Sulfonation temperature is too high, then causes the Ti/C hybrid material easily to continue to be carbonized, to dissolve, and destroys the overall structure of solid acid.And in sulfonation temperature scope of the present invention, sulfonation temperature is higher, and the acidity of carbon-based solid acid is stronger.
Another object of the present invention is to provide a kind of Ti/C hydridization carbon-based solid acid catalyst by the said method preparation.
Ti/C hydridization carbon-based solid acid catalyst by preparation method's preparation of the present invention is applicable to the catalytic hydrolysis reaction system, be specially adapted to reaction substrate and be the catalytic hydrolysis reaction system of the polysaccharose substances such as the lipids such as Ethyl formate, ethyl acetate, ethyl propionate or starch, sucrose, cellulose, reaction substrate is preferably starch or sucrose.
Beneficial effect
The catalyst raw material is inexpensive among the preparation method of the present invention, and has used the catalytic hydrolysis reaction system safety non-pollution of catalyst, and the catalytic activity of prepared catalyst is high.Behind the catalytic hydrolysis reaction, catalyst is easy to recycle, and product separates automatically with catalyst, is easy to extract, and reaction condition is gentle, is easy to realize industrial applications.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.But it should be understood that following examples are only for explanation the present invention but not for limiting scope of the present invention.
Embodiment 1
The 0.8g isopropyl titanate is dissolved in the 30mL ethanol, then 0.5g absorbent cotton is impregnated in the mentioned solution, at 180 ℃ reactor reaction 12h.The material that reaction is obtained obtains the Ti/C hybrid material at 400 ℃ of lower carbonization 1h, then is placed in 50% oleum, behind 120 ℃ of lower sulfonation 10h, washs extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
The test of nitrogen adsorption desorption is carried out at the ASAP2020M+C physical analystical instrument,, adsorbs the specific area of working sample under liquid nitrogen temperature take nitrogen as adsorbate.The specific area that records this Ti/C hydridization carbon-based solid acid catalyst of gained is 13.9m
2G
-1, and under the same terms, the specific area of the carbon-based solid acid that mixes without Ti is almost 0.
Embodiment 2
The 0.8g isopropyl titanate is dissolved in the 30mL ethanol, and 0.5g absorbent cotton impregnated in mentioned solution at 180 ℃ reactor reaction 12h.650 ℃ of carbonization 1h of material that reaction is obtained obtain the Ti/C hybrid material, then are placed in 50% oleum, behind 140 ℃ of lower sulfonation 10h, wash extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
Embodiment 3
The 0.8g butyl titanate is dissolved in the 30mL ethanol, and 0.5g absorbent cotton impregnated in mentioned solution, at 180 ℃ reactor reaction 12h.400 ℃ of carbonization 1h of Ti/C hybrid material that reaction is obtained obtain the Ti/C hybrid material, then are placed in 50% oleum, behind 120 ℃ of lower sulfonation 10h, wash repeatedly extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
The catalytic hydrolysis reaction experiment
Embodiment 4
With 0.2g starch, the Ti/C hydridization carbon-based solid acid catalyst of 0.05g embodiment 1 and 2mL distilled water mix and add test tube, and 45w power is warming up to 100 ℃ of reaction 45min under the microwave condition.Reaction finishes rear catalyst and becomes whole group's cotton shape to separate with reaction system.Adopt the glucose ELIASA to measure the product concentration of glucose.
The used standard liquid of test was the glucose solution of 0.01g/mL during the glucose ELIASA was measured, and therefore, was that the standard of 0.01g/mL is come dilute solution with solution according to starch concentration at first, this experiment be with reactant liquor with ten times of distilled water dilutings as liquid to be measured.
Specifically carry out in accordance with the following steps:
1, calibrates, get the glucose solution of the 0.01g/mL of 25uL, instrument display 100.
2, get 25uL liquid to be measured, read the numerical value of instrument display.
Starch Hydrolysis rate %=(n
1 glucose/ n
2 glucose) * 100%
N wherein
1 glucoseRepresent the amount of substance of the actual glucose that obtains, unit is mol; n
2 glucoseThe amount of substance of the glucose that Starch Hydrolysis obtains on the representation theory, the mol of unit.
Calculate the Starch Hydrolysis rate and reach 72%.
Embodiment 5
With 0.2g starch, the Ti/C hydridization carbon-based solid acid catalyst of 0.05g embodiment 1 and 2mL distilled water mix and add test tube, and 45w power is warming up to 120 ℃ of reaction 45min under the microwave condition.Reaction finishes rear catalyst and becomes whole group's cotton shape to separate with reaction system.Adopt the glucose ELIASA to measure the product concentration of glucose, measuring method is with described in the embodiment 4.
Starch Hydrolysis rate %=(n
1 glucose/ n
2 glucose) * 100%
N wherein
1 glucoseRepresent the amount of substance of the actual glucose that obtains, unit is mol; n
2 glucoseThe amount of substance of the glucose that Starch Hydrolysis obtains on the representation theory, the mol of unit.
Calculate the Starch Hydrolysis rate and reach 87%.
Embodiment 6
With 0.2g starch, the Ti/C hydridization carbon-based solid acid catalyst of 0.05g embodiment 2 and 2mL distilled water mix and add test tube, and 45w power is warming up to 120 ℃ of reaction 45min under the microwave condition.Reaction finishes rear catalyst and becomes whole group's cotton shape to separate with reaction system.Adopt the glucose ELIASA to measure the product concentration of glucose, measuring method is with described in the embodiment 4.
Starch Hydrolysis rate %=(n
1 glucose/ n
2 glucose) * 100%
N wherein
1 glucoseRepresent the amount of substance of the actual glucose that obtains, unit is mol; n
2 glucoseThe amount of substance of the glucose that Starch Hydrolysis obtains on the representation theory, the mol of unit.
Calculate the Starch Hydrolysis rate and reach 100%.
Embodiment 7
With 0.02g sucrose, the Ti/C hydridization carbon-based solid acid catalyst of 0.02g embodiment 2 and 1mL distilled water mix and add test tube, and 30w power is warming up to 75 ℃ of reaction 1.5h under the microwave condition.Reaction finishes rear catalyst and becomes whole group's cotton shape to separate with reaction system.Adopt the glucose ELIASA to measure the product concentration of glucose.
Testing the glucose solution that used standard liquid is 0.01g/mL, therefore, is that the standard of 0.01g/mL is come dilute solution with solution according to sucrose concentration at first, this experiment be with reactant liquor with two times of distilled water dilutings as liquid to be measured.
Specifically carry out in accordance with the following steps:
1, calibration, the glucose solution of 25uL0.01g/mL, instrument display 100.
2, get 25uL liquid to be measured, read the numerical value of instrument display.
Sucrose hydrolysis rate %=(n
1 glucose/ n
2 glucose) * 100%
N wherein
1 glucoseRepresent the amount of substance of the actual glucose that obtains, unit is mol; n
2 glucoseThe amount of substance of the glucose that Starch Hydrolysis obtains on the representation theory, the mol of unit.
Calculate the sucrose hydrolysis rate and reach 100%.
Embodiment 8
With 0.02g sucrose, the Ti/C hydridization carbon-based solid acid catalyst of 0.02g embodiment 3 and 1mL distilled water mix and add test tube, and 30w power is warming up to 75 ℃ of reaction 1.5h under the microwave condition.Reaction finishes rear catalyst and becomes whole group's cotton shape to separate with reaction system.Adopt the glucose ELIASA to measure the product concentration of glucose, measuring method is with described in the embodiment 7.
Sucrose hydrolysis rate %=(n
1 glucose/ n
2 glucose) * 100%.
N wherein
1 glucoseRepresent the amount of substance of the actual glucose that obtains, unit is mol; n
2 glucoseThe amount of substance of the glucose that Starch Hydrolysis obtains on the representation theory, the mol of unit.
Calculate the sucrose hydrolysis rate and reach 90%.
Ti/C hydridization carbon-based solid acid catalyst of the present invention is that the catalytic hydrolysis reaction system of the polysaccharose substances such as the lipids such as Ethyl formate, ethyl acetate, ethyl propionate or starch, sucrose, cellulose has higher catalytic activity to reaction substrate as can be seen from the above embodiments, can realize larger percent hydrolysis.
Above embodiment enumerates as the example of embodiment of the present invention, the present invention is not consisted of any restriction, it will be appreciated by those skilled in the art that the modification in the scope that does not depart from essence of the present invention and design all falls into protection scope of the present invention.
Claims (10)
1. the preparation method of a Ti/C hydridization carbon-based solid acid catalyst said method comprising the steps of:
1) in organic solvent with absorbent cotton and titaniferous presoma in mass ratio 5:2-20 mix, then in 150 ℃ to 250 ℃ temperature range, heat, reacted 0.5 to 24 hour;
2) with the at a certain temperature carbonization of mixture that obtains in the step 1);
3) to step 2) in add sulfonating agent in the product that obtains and carry out sulfonation; With
4) washing step 3) in the product that obtains to without SO
4 2-
2. preparation method according to claim 1, it is characterized in that, used organic solvent comprises and is selected from methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol and the isobutanol one or more in the described step 1), be preferably methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, more preferably ethanol; The mass ratio of absorbent cotton and titaniferous presoma is preferably 5:2-15, and more preferably 5:2-10 most preferably is 5:8;
Described titaniferous presoma is to be selected from tetraethyl titanate, butyl titanate, isopropyl titanate and the metatitanic acid monooctyl ester one or more, is preferably tetraethyl titanate, butyl titanate, isopropyl titanate; More preferably butyl titanate and isopropyl titanate;
Reaction temperature is preferably 160 ℃ to 200 ℃ scope in the described step 1), more preferably 180 ℃; Reaction is preferably 1 to 20 hour, more preferably 5 to 15 hours, most preferably is 12 hours.
3. preparation method according to claim 1 is characterized in that, described step 2) in carburizing temperature be 400 ℃ to 700 ℃, be preferably 400 ℃ to 650 ℃, more preferably carbonization time is 0.5 to 4 hour.
4. preparation method according to claim 1, it is characterized in that, the sulfonating agent that adopts in the described step 3) is selected from 98% concentrated sulfuric acid, 20% oleum or 50% oleum, sulfonation temperature is 60 ℃ to 160 ℃, be preferably 120 ℃ to 140 ℃, the sulfonation time is 4 to 16 hours, is preferably 8 to 12 hours.
5. preparation method according to claim 1 is characterized in that, then described method impregnated in 0.5g absorbent cotton in the mentioned solution for the 0.8g isopropyl titanate is dissolved in the 30mL ethanol, at 180 ℃ reactor reaction 12h; The material that reaction is obtained obtains the Ti/C hybrid material at 400 ℃ of lower carbonization 1h, then is placed in 50% oleum, behind 120 ℃ of lower sulfonation 10h, washs extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
6. preparation method according to claim 1 is characterized in that, described method is for to be dissolved in the 0.8g isopropyl titanate in the 30mL ethanol, and 0.5g absorbent cotton impregnated in mentioned solution, at 180 ℃ reactor reaction 12h; 650 ℃ of carbonization 1h of material that reaction is obtained obtain the Ti/C hybrid material, then are placed in 50% oleum, behind 140 ℃ of lower sulfonation 10h, wash extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
7. preparation method according to claim 1 is characterized in that, described method is for to be dissolved in the 0.8g butyl titanate in the 30mL ethanol, and 0.5g absorbent cotton impregnated in mentioned solution, at 180 ℃ reactor reaction 12h; 400 ℃ of carbonization 1h of Ti/C hybrid material that reaction is obtained obtain the Ti/C hybrid material, then are placed in 50% oleum, behind 120 ℃ of lower sulfonation 10h, wash repeatedly extremely without SO with 85 ℃ of distilled water
4 2-About 60 ℃ of dry 10h, namely get cotton bulk Ti/C hydridization carbon-based solid acid.
8. Ti/C hydridization carbon-based solid acid catalyst by any one preparation in the claim 1 to 7.
9. the purposes of the Ti/C hydridization carbon-based solid acid catalyst described in according to claim 8 is characterized in that described catalyst is used for the catalytic hydrolysis reaction system that reaction substrate is the polysaccharose substances such as the lipid such as Ethyl formate, ethyl acetate, ethyl propionate or starch, sucrose, cellulose.
10. purposes according to claim 9,, the reaction substrate that it is characterized in that described catalytic hydrolysis reaction system is starch or sucrose.
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| CN113385197A (en) * | 2021-06-16 | 2021-09-14 | 华东理工大学 | Zirconium dioxide and titanium dioxide doped solid acid catalyst and application thereof |
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Effective date of registration: 20130516 Address after: 266101 Shandong Province, Qingdao city Laoshan District Songling Road No. 189 Applicant after: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences Applicant after: Qingdao University of Science & Technology Address before: 266101 Shandong Province, Qingdao city Laoshan District Songling Road No. 189 Applicant before: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences |
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Application publication date: 20130501 |