CN105148990A - Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst - Google Patents
Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method and an application of a sulfated carbon nanotube/graphene oxide composite catalyst, and belongs to the technical field of catalytic fine industrial chemistry. According to the invention, sulfated carbon nanotube is compounded with graphene oxide to improve the yield of an esterification reaction of reaction substances, the structures of which are characterized by long-carbon-chain carboxylic acid and fatty alcohol, thereby replacing traditional catalysts of inorganic strong acid, such as protonic acid of concentrated sulfuric acid and hydrochloric acid, and greatly simplifying the whole period of the esterification reaction. The result shows that under the condition of same reaction selectivity and yield of a catalytic reaction, the sulfated carbon nanotube/graphene oxide composite catalyst provided in the invention is low in added amount, and can greatly reduce the industrial production cost. After the reaction is over, the composite catalyst can be directly recycled and utilized through simple filtering, and still has a preferable catalytic effect after repeated use.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of sulfonated CNT/graphene oxide composite catalyst, prepared sulfonated CNT/graphene oxide composite catalyst can be used for the esterification of Long carbon chain carboxylic acid and fatty alcohol, belongs to catalysis technical field of fine.
Background technology
Esterification is the very important organic synthesis of a class in chemical industry.And wherein, catalyst plays a very important role.In current esterification, main use have inorganic acid, solid super-strong acid [Xiong Sen, Wu Hongte, Yu Bingchuan. presence of compound solid superacid catalyst esterification progress [J]. chemistry and bioengineering, 2013, 30 (3): 10-13.], heteropoly acid [Jiang Pingping. esterification catalyst research progress and prospect [J]. plasticizer, 2000 (1): 8-12.], ion exchange resin [MaL, HanY, SunK, etal.Optimizationofacidifiedoilesterificationcatalyzedby sulfonatedcationexchangeresinusingresponsesurfacemethodo logy [J] .EnergyConversionandManagement, 2015, 98:46-53.], ionic liquid [FauziAHM, AminNAS, MatR.Esterificationofoleicacidtobiodieselusingmagneticio nicliquid:multi-objectiveoptimizationandkineticstudy [J] .AppliedEnergy, 2014, 114:809-818.] etc. esterification catalyst.And in Chemical Manufacture, the most widely used, be the concentrated sulfuric acid in inorganic acid classification, its advantage is that catalytic activity is high, with low cost.But in the process using strong sulfuric acid response, equipment corrosion is serious, can produce a large amount of spent acid contaminated environment after the completion of reaction.Therefore, environmental protection and highly active catalyst for esterification reaction become the focus of research and development.
Sulfonic acid type solid acid catalyst, as a kind of novel environment-friendly type esterification catalyst, obtains and pays close attention to more and more widely, and it and reaction system compatibility are good, and reaction speed is fast, and product form and aspect meet the requirements and to be cheaply easy to get.Sulphonic acids catalyst is easy to regeneration, and reaction temperature is low, and product quality and color and luster are all better than inorganic acid catalyst, and catalyst performance and reaction yield are also higher.
Graphene oxide, CNT [MaitiUN, LeeWJ, LeeJM, etal.Carbon:25thAnniversaryArticle:ChemicallyModified/Do pedCarbonNanotubes & GrapheneforOptimizedNanostructures & Nanodevices [J] .AdvancedMaterials, 2014, 26 (1): 2-2.] this class material with carbon element causes the extensive concern of lot of domestic and foreign scholar from 21 century, the wherein electric conductivity of graphene oxide superelevation, high specific area and its stable performance, for it has won one seat in the extensive use of chemical field.Graphene oxide is as catalyst [Zhang Li, Gao Shutao, Liu Weihua, Deng. Graphene and composite thereof the New research progress in catalyse organic reaction [J]. organic chemistry, 2014:0-0.] be widely studied at chemical field, its huge specific area, for the load of catalyst and the raising [Yuan Dingchong of activity, Chen Bibo. the synthesis of graphene oxide-loaded Schiff-base Palladium catalyst, sign and the research [J] to Suzuki reacting catalytic performance. organic chemistry, 2014:0-0.] provide good condition.CNT/graphene oxide the composite catalyst of the bigger serface sulfonic acid group grafting that the present invention is successfully prepared, has higher catalyzing esterification active, and there is no bibliographical information.
Summary of the invention
The object of the invention is, for current Long carbon chain esterification conversion ratio and the lower technical bottleneck problem of yield, to prepare a kind of CNT/graphene oxide composite catalyst of sulfonic acid group grafting, thus improve its esterification yied.Preparation method's environmental protection of this composite catalyst, and the composite catalyst reusable edible of preparation, still have higher catalytic activity after recovery.
Technical scheme of the present invention, a kind of preparation method of sulfonated CNT/graphene oxide composite catalyst, step is:
(1) get 1-5g sodium p styrene sulfonate to be dissolved in 100mL distilled water, add 20-100mg multi-walled carbon nano-tubes, use 50KHz supersonic wave cleaning machine continuous ultrasound 1-2h, subsequently with the rotating speed uniform stirring 3-5h of 300-500rpm; Moved in there-necked flask by mixture after stirring, add 0.2-1g potassium peroxydisulfate, and remove oxygen in system with the method that bubble type leads to nitrogen, the time maintains 30-60min; Reaction system is slowly warming up to 90 DEG C, with the rotating speed uniform stirring 4-6h of 500-800rpm;
(2) after reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5-8 time; Filter in gained solid and add the concentrated hydrochloric acid that 50mL mass concentration is 35%-37.5%, condensing reflux 8h at the temperature of 70-100 DEG C;
(3) step (2) gained solution is reused mixed fine membrane filtration, finally spend deionized water 5-10 time, gained solid matter is placed in vacuum drying chamber, and under-0.1MPa, 50-70 DEG C is dried 10h, and gained atrament is sulfonated modified carbon nano-tube;
(4) the sulfonated modified carbon nano-tube 40mg that step (3) is obtained is mixed with graphene oxide 20-100mg, join in 100mL ethanol, use 50KHz supersonic wave cleaning machine continuous ultrasound 10-30min, at 90-130 DEG C of temperature, add hot reflux 1-2h subsequently; Backflow terminates step in rear repetition step (3) and reuses mixed fine membrane filtration, finally spend deionized water 5-10 time, gained solid matter is placed in vacuum drying chamber, under-0.1MPa, 50-70 DEG C is dried 10h, and last gained black solid material is product sulfonated CNT/graphene oxide composite catalyst.
In step (1), sodium p styrene sulfonate purity is 90%-99.99%.
Use water system to mix fine filter membrane, pore size is 0.30-0.50 μm.
The application of described sulfonated CNT/graphene oxide composite catalyst: for the esterification of Long carbon chain carboxylic acid and fatty alcohol, be the dehydration of Long carbon chain carboxylic acid and fatty alcohol, reaction equation is as follows:
R
1for the alkyl of carbon atom>=10, comprise double bond alkyl, phenyl ring and substituted benzene ring; R
2for the alkyl of carbon number>=8 and hydroxyl in end position.
Obtained sulfonated CNT/graphene oxide composite catalyst is used in the reaction of higher fatty acids laurate and isooctanol.Concrete steps are: in 25mL there-necked flask, add 4g laurate, 10mL isooctanol, add 2wt% sulfonated CNT/graphene oxide composite catalyst, normal pressure 90 DEG C reaction 6h, observe every 0.5h sampling, standard acid-base titrimetric method is adopted to measure the change of its reaction yield, finally prove by gas-chromatography, record esterification yied.
Beneficial effect of the present invention: the present invention uses sulfonic acid group as catalytic reaction activity center, on the immobilized carrier in having bigger serface, can reduce the pollution of monomer sulfonic acid class catalyst for environment greatly; Prepared catalyst is used for liquid-solid phase reaction, is convenient to be separated after reaction, and can recycled for multiple times, greatly reduces factory cost; Adopt novel CNT/graphene oxide as the carrier of catalyst, increase substantially the catalytic efficiency of catalyst, other sulphonic acids esterification catalysts of the same type of comparing, have higher esterification yied and reaction selectivity.Sulfonated CNT/graphene oxide composite catalyst prepared by the present invention, can be used for the esterification of Long carbon chain carboxylic acid and fatty alcohol, and reaction yield is higher, solves the Long carbon chain carboxylic acid technical barrier that productive rate is lower in the esterification reaction in industrial production.
Accompanying drawing explanation
Fig. 1 is laurate and isooctanol productive rate change curve in time when using different catalysts.
Detailed description of the invention
Below in conjunction with some examples and accompanying drawing, the present invention will be further described, but interest field of the present invention is not limited only to the scope of example.
Embodiment 1
Get 1g sodium p styrene sulfonate to be dissolved in 100mL distilled water, add 50mg multi-walled carbon nano-tubes, 50KHz ultrasonic 1h, 300-500rpm stir 3h; Mixture after stirring is moved in there-necked flask, adds 0.5g potassium peroxydisulfate, and maintaining nitrogen purge 30min, remove the oxygen in reaction system; Subsequently there-necked flask is put into oil bath pan, be slowly warming up to 90 DEG C, 500-800rpm uniform stirring 4h; After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Subsequently filtration gained solid matter is added in the concentrated hydrochloric acid of 50mL35%-37.5%, condensing reflux 8h at 80 DEG C; Again filtered by solution, finally spend deionized water 5 times, by solid vacuum drying, gained atrament is sulfonated modified carbon nano-tube.Get sulfonated modified carbon nano-tube 40mg to mix with 40mg graphene oxide, add 100mL ethanol, be placed in 250mL there-necked flask, the ultrasonic 30min of 50KHz, 100 DEG C add hot reflux 2h; After backflow terminates, by the mixed fine membrane filtration of solution, spend deionized water 5 times, by solid vacuum drying, finally obtain sulfonated CNT/graphene oxide composite catalyst.
Obtained sulfonated CNT/graphene oxide composite catalyst is used in the reaction of higher fatty acids laurate and isooctanol.4g laurate, 10mL isooctanol is added in 25mL there-necked flask, add 2wt% sulfonated CNT/graphene oxide composite catalyst, normal pressure 90 DEG C reaction 6h, observe every 0.5h sampling, standard acid-base titrimetric method is adopted to measure the change of its reaction yield, finally prove by gas-chromatography, recording esterification yied is 43.25%.Adopt same procedure, use the dense H of 2wt%
2sO
4as catalyst, finally recording esterification yied is 28.36%, and the sulfonated CNT/graphene oxide composite catalyst prepared by us in contrast to traditional dense H
2sO
4, productive rate improves 0.5 times.
Embodiment 2
Getting 2g sodium p styrene sulfonate is dissolved in 100mL distilled water, adds 50mg multi-walled carbon nano-tubes subsequently, and 50KHz ultrasonic 1h, 300-500rpm stir 3h; Mixture after stirring is moved in there-necked flask, adds 0.5g potassium peroxydisulfate, and continue to pass into nitrogen 30min, remove the oxygen in reaction system; Subsequently there-necked flask is put into oil bath pan, be slowly warming up to 90 DEG C, 500-800rpm uniform stirring 4h; After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Subsequently filtration gained solid matter is added in the concentrated hydrochloric acid of 50mL35%-37.5%, condensing reflux 8h at 80 DEG C; Again filtered by solution, finally spend deionized water 5 times, by solid vacuum drying, gained atrament is sulfonated modified carbon nano-tube.Get sulfonated modified carbon nano-tube 40mg to mix with 60mg graphene oxide, add 100mL ethanol, be placed in 250mL there-necked flask, the ultrasonic 30min of 50KHz, 90 DEG C add hot reflux 2h; After backflow terminates, by the mixed fine membrane filtration of solution, spend deionized water 5 times, by solid vacuum drying, finally obtain sulfonated CNT/graphene oxide composite catalyst.
Obtained sulfonated CNT/graphene oxide composite catalyst is used in the reaction of higher fatty acids laurate and isooctanol.Carry out according to method described in embodiment 1, after reaction 6h, ultimate yield is 49.13%.Dense H in comparative example 1
2sO
4productive rate, improves 0.73 times.
Embodiment 3
Getting 5g sodium p styrene sulfonate is dissolved in 100mL distilled water, adds 100mg multi-walled carbon nano-tubes subsequently, and 50KHz ultrasonic 1h, 300-500rpm stir 3h; Mixture after stirring is moved in there-necked flask, adds 0.5g potassium peroxydisulfate, and continue to pass into nitrogen 30min, remove the oxygen in reaction system; Subsequently there-necked flask is put into oil bath pan, be slowly warming up to 90 DEG C, 500-800rpm uniform stirring 4h; After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Subsequently filtration gained solid matter is added in the concentrated hydrochloric acid of 50mL35%-37.5%, condensing reflux 8h at 80 DEG C; Again filtered by solution, finally spend deionized water 5 times, by solid vacuum drying, gained atrament is sulfonated modified carbon nano-tube.Get sulfonated modified carbon nano-tube 40mg to mix with 60m graphene oxide, add 100mL ethanol, be placed in 250mL there-necked flask, the ultrasonic 30min of 50KHz, 110 DEG C add hot reflux 2h; After backflow terminates, by the mixed fine membrane filtration of solution, spend deionized water 5 times, by solid vacuum drying, finally obtain sulfonated CNT/graphene oxide composite catalyst.
Obtained sulfonated CNT/graphene oxide composite catalyst is used in the reaction of higher fatty acids laurate and isooctanol.Carry out according to method described in embodiment 2, after normal pressure 90 DEG C reaction 6h, ultimate yield is 52.12%.Dense H in comparative example 1
2sO
4productive rate, improves 0.84 times.
Embodiment 4
Sulfonated CNT/graphene oxide composite catalyst is prepared according to embodiment 2, be applied in the reaction of higher fatty acids laurate and isooctanol, 4g laurate is added in 25mL there-necked flask, 10mL isooctanol, add 2wt% sulfonated CNT/graphene oxide composite catalyst, normal pressure, reduce reaction temperature to 60 DEG C, reaction 6h, observe every 0.5h sampling, adopt standard acid-base titrimetric method to measure the change of its reaction yield, finally prove by gas-chromatography, recording final esterification yied is 43.94%.
Embodiment 5
The higher fatty acids laurate and isooctanol that do not add composite catalyst of the present invention are reacted according to the method for embodiment 2, recording blank esterification yied is 19.37%.
Embodiment 6
Purchase commercially available sulphonic acids solid acid esterification catalyst, use it for the reaction of higher fatty acids laurate and isooctanol, react according to embodiment 2 method, recording ultimate yield is 35.23%.
By embodiment 2, embodiment 6 and dense H
2sO
4these three kinds of different catalysts contrast with blank reaction, by laurate and isooctanol productive rate in time change curve drafting pattern 1 intuitively contrast.
Can be found out by the various embodiments described above and Fig. 1, the novel sulfonated CNT/graphene oxide composite catalyst prepared by the present invention contrasts the catalyst that other catalyst of the same type and market are sold, and all has a clear superiority in.Show in Fig. 1, after reaction 1.5h, esterification yied is close to 40%, composite catalyst reactivity prepared by visible the present invention is higher, being applied to can be significantly cost-saving in industrial production, and asepsis environment-protecting, be a kind of new catalytic material having larger industrial esterification application prospect.
Claims (5)
1. a preparation method for sulfonated CNT/graphene oxide composite catalyst, is characterized in that step is:
(1) get 1-5g sodium p styrene sulfonate to be dissolved in 100mL distilled water, add 20-100mg multi-walled carbon nano-tubes, use 50KHz supersonic wave cleaning machine continuous ultrasound 1-2h, subsequently with the rotating speed uniform stirring 3-5h of 300-500rpm; Moved in there-necked flask by mixture after stirring, add 0.2-1g potassium peroxydisulfate, and remove oxygen in system with the method that bubble type leads to nitrogen, the time maintains 30-60min; Reaction system is slowly warming up to 90 DEG C, with the rotating speed uniform stirring 4-6h of 500-800rpm;
(2) after reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5-8 time; Filter in gained solid and add the concentrated hydrochloric acid that 50mL mass concentration is 35%-37.5%, condensing reflux 8h at the temperature of 70-100 DEG C;
(3) step (2) gained solution is reused mixed fine membrane filtration, finally spend deionized water 5-10 time, gained solid matter is placed in vacuum drying chamber, and under-0.1MPa, 50-70 DEG C is dried 10h, and gained atrament is sulfonated modified carbon nano-tube;
(4) the sulfonated modified carbon nano-tube 40mg that step (3) is obtained is mixed with graphene oxide 20-100mg, join in 100mL ethanol, use 50KHz supersonic wave cleaning machine continuous ultrasound 10-30min, at 90-130 DEG C of temperature, add hot reflux 1-2h subsequently; Backflow terminates step in rear repetition step (3) and reuses mixed fine membrane filtration, finally spend deionized water 5-10 time, gained solid matter is placed in vacuum drying chamber, under-0.1MPa, 50-70 DEG C is dried 10h, and last gained black solid material is product sulfonated CNT/graphene oxide composite catalyst.
2. the preparation method of sulfonated CNT/graphene oxide composite catalyst according to claim 1, is characterized in that: in step (1), sodium p styrene sulfonate purity is 90%-99.99%.
3. the preparation method of sulfonated CNT/graphene oxide composite catalyst according to claim 1, is characterized in that: use water system to mix fine filter membrane, pore size is 0.30-0.50 μm.
4. the application of the sulfonated CNT/graphene oxide composite catalyst prepared by method described in claim 1, is characterized in that: for the esterification of Long carbon chain carboxylic acid and fatty alcohol, be the dehydration of Long carbon chain carboxylic acid and fatty alcohol, reaction equation is as follows:
R
1for the alkyl of carbon atom>=10, comprise double bond alkyl, phenyl ring and substituted benzene ring; R
2for the alkyl of carbon number>=8 and hydroxyl in end position.
5. the application of sulfonated CNT/graphene oxide composite catalyst as claimed in claim 4, obtained sulfonated CNT/graphene oxide composite catalyst is it is characterized in that to be used in the reaction of higher fatty acids laurate and isooctanol, concrete steps are: in 25mL there-necked flask, add 4g laurate, 10mL isooctanol, add 2wt% sulfonated CNT/graphene oxide composite catalyst, normal pressure 90 DEG C reaction 6h, observe every 0.5h sampling, standard acid-base titrimetric method is adopted to measure the change of its reaction yield, finally prove by gas-chromatography, record esterification yied.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944133A (en) * | 2017-04-17 | 2017-07-14 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid catalyst and its preparation method and application |
| CN107199050A (en) * | 2017-04-17 | 2017-09-26 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN107236139A (en) * | 2017-06-16 | 2017-10-10 | 青岛大学 | A kind of high-performance carbon nanotube/graphite oxide aerogel/poly styrene composite material and preparation method thereof |
| CN108251076A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube-graphene composite radiating film, preparation method and application |
| CN109111361A (en) * | 2018-10-08 | 2019-01-01 | 扬州工业职业技术学院 | A kind of method that one-step method efficiently prepares the dodecyl diacid list tert-butyl ester |
| CN109825263A (en) * | 2019-04-12 | 2019-05-31 | 西南石油大学 | A kind of water-base drilling fluid nanometer sealing agent and preparation method thereof and drilling fluid |
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| CN108251076A (en) * | 2016-12-29 | 2018-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube-graphene composite radiating film, preparation method and application |
| CN106944133A (en) * | 2017-04-17 | 2017-07-14 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid catalyst and its preparation method and application |
| CN107199050A (en) * | 2017-04-17 | 2017-09-26 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN107199050B (en) * | 2017-04-17 | 2019-11-19 | 浙江工业大学 | A kind of sulfonic acid carbon nano tube solid acid and its preparation method and application |
| CN107236139A (en) * | 2017-06-16 | 2017-10-10 | 青岛大学 | A kind of high-performance carbon nanotube/graphite oxide aerogel/poly styrene composite material and preparation method thereof |
| CN107236139B (en) * | 2017-06-16 | 2020-02-07 | 青岛大学 | High-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material and preparation method thereof |
| CN109111361A (en) * | 2018-10-08 | 2019-01-01 | 扬州工业职业技术学院 | A kind of method that one-step method efficiently prepares the dodecyl diacid list tert-butyl ester |
| CN109825263A (en) * | 2019-04-12 | 2019-05-31 | 西南石油大学 | A kind of water-base drilling fluid nanometer sealing agent and preparation method thereof and drilling fluid |
| CN109825263B (en) * | 2019-04-12 | 2021-11-02 | 西南石油大学 | Nano plugging agent for water-based drilling fluid, preparation method of nano plugging agent and drilling fluid |
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