CN105148990B - A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst - Google Patents
A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst Download PDFInfo
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- CN105148990B CN105148990B CN201510473014.XA CN201510473014A CN105148990B CN 105148990 B CN105148990 B CN 105148990B CN 201510473014 A CN201510473014 A CN 201510473014A CN 105148990 B CN105148990 B CN 105148990B
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Abstract
A kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst, belong to catalysis technical field of fine.After sulfonated CNT and graphene oxide are combined by the present invention, it is Long carbon chain carboxylic acid and the esterification yield of fatty alcohol for improving reaction substrate architectural feature, so as to substitute traditional strong inorganic acid catalyst, such as the Bronsted acid concentrated sulfuric acid, hydrochloric acid, and enormously simplify the whole esterification cycle.As a result prove, in the case of catalytic reaction selectivity and yield identical, sulfonic acid carbon nano tube/graphene oxide composite catalyst dosage that the present invention is provided is small, and industrial production cost can be greatly lowered；After reaction terminates, the composite catalyst just can be recycled directly by simple filtration, and through being used for multiple times, still with preferable catalytic effect.
Description
Technical field
The present invention relates to a kind of preparation method and applications of sulfonic acid carbon nano tube/graphene oxide composite catalyst,
Prepared sulfonic acid carbon nano tube/graphene oxide composite catalyst can be used for the esterification of Long carbon chain carboxylic acid and fatty alcohol anti-
Should, belong to catalysis technical field of fine.
Background technology
Esterification is the highly important organic synthesis of a class in chemical industry.And wherein, catalyst plays ten
Divide important effect.In current esterification, the presence or absence of mainly use machine acid, solid super-strong acid [Xiong Sen, Wu Hongte, in
Soldier river presence of compound solid superacid catalyst esterification progress [J] chemistry and bioengineering, 2013,30 (3): 10-
13.], heteropoly acid [Jiang Pingping esterification catalysts research progress and prospect [J] plasticizer, 2000 (1): 8-12. ]、
Ion exchange resin [Ma L, Han Y, Sun K, et al. Optimization of acidified oil
esterification catalyzed by sulfonated cation exchange resin using response
surface methodology [J]. Energy Conversion and Management, 2015, 98: 46-53.
], ionic liquid [Fauzi A H M, Amin N A S, Mat R. Esterification of oleic acid to
biodiesel using magnetic ionic liquid: multi-objective optimization and
kinetic study [J]. Applied Energy, 2014, 114:809-818.] etc. esterification catalyst.And in chemical industry
It is the most widely used in production, it is the concentrated sulfuric acid in inorganic acid classification, its advantage is that catalytic activity is high, with low cost.But
During using strong sulfuric acid response, equipment corrosion is serious, and substantial amounts of spent acid pollution environment can be produced after the completion of reaction.Cause
This, the catalyst for esterification reaction of environmental protection and high activity becomes the focus of research and development.
Sulfonic acid type solid acid catalyst, as a kind of new environment-friendly type esterification catalyst, has been obtained more and more extensive
Concern, it is good with reaction system compatibility, and soon, product form and aspect meet the requirements and cheap are easy to get reaction speed.Sulphonic acids
Catalyst is easy to regeneration, and reaction temperature is low, and product quality and color and luster are superior to inorganic acid catalyst, and catalyst performance and reaction are received
Rate is also higher.
Graphene oxide, CNT [Maiti U N, Lee W J, Lee J M, et al. Carbon: 25th
Anniversary Article: Chemically Modified/Doped Carbon Nanotubes & Graphene
for Optimized Nanostructures & Nanodevices [J]. Advanced Materials, 2014, 26
(1):2-2.] this class carbon material causes the extensive concern of lot of domestic and foreign scholar since 21 century, wherein aoxidizing stone
Electric conductivity, high specific surface area and its stable performance of black alkene superelevation, are that it wins in the extensive use of chemical field
One seat.As catalyst, [Zhang Li, Gao Shutao, Liu Weihua wait graphenes and its composite to graphene oxide
New research progress [J] organic chemistry in catalysis organic reaction, 2014:0-0.] ground extensively in chemical field
Study carefully, its huge specific surface area, be catalyst load and activity raising [Yuan Dingchong, Chen Bibo are graphene oxide-loaded
The synthesis of Schiff-base Palladium catalyst, is characterized and to research [J] organic chemistry of Suzuki reacting catalytic performances, 2014: 0-
0.] good condition is provided.CNT/oxidation stone of bigger serface sulfonic acid group grafting prepared by present invention success
Black alkene composite catalyst, with higher catalyzing esterification activity, and there is no literature reported on.
The content of the invention
The purpose of the present invention is to be directed to current Long carbon chain esterification conversion ratio and the relatively low technical bottleneck problem of yield, system
The standby a kind of CNT of sulfonic acid group grafting/graphene oxide composite catalyst, so as to improve its esterification yied.This is combined and urged
The preparation method environmental protection of agent, and the composite catalyst reusable edible prepared, still have higher catalysis after recovery
Activity.
Technical scheme, a kind of preparation method of sulfonic acid carbon nano tube/graphene oxide composite catalyst, step
Suddenly it is：
（1）Take 1-5g sodium p styrene sulfonates to be dissolved in 100mL distilled water, add 20-100mg multi-walled carbon nanotubes, make
With 50KHz supersonic wave cleaning machine continuous ultrasound 1-2h, then with 300-500rpm rotating speed uniform stirring 3-5h；After stirring
Mixture is moved into three-necked flask, adds 0.2-1g potassium peroxydisulfates, and with oxygen in the method removal system of the logical nitrogen of bubble type,
Time maintains 30-60min；Reaction system is to slowly warm up to 90 DEG C, with 500-800rpm rotating speed uniform stirring 4-6h；
（2）After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5-8 times；Added in filtering gained solid
50mL mass concentrations are 35%-37.5% concentrated hydrochloric acid, the condensing reflux 8h at a temperature of 70-100 DEG C；
（3）By step（2）Resulting solution reuses mixed fine membrane filtration, is finally washed with deionized 5-10 times, will
Gained solid matter is placed in vacuum drying chamber, and the 50-70 DEG C of baking 10h under -0.1MPa, gained atrament is as sulfonated
Modified carbon nano-tube；
（4）By step（3）Obtained sulfonated modified carbon nano-tube 40mg is mixed with graphene oxide 20-100mg, is added
Into 100mL ethanol, using 50KHz supersonic wave cleaning machine continuous ultrasound 10-30min, then heated at a temperature of 90-130 DEG C
Flow back 1-2h；Backflow terminates rear repeat step（3）Middle step reuses mixed fine membrane filtration, and 5- is finally washed with deionized
10 times, gained solid matter is placed in vacuum drying chamber, 50-70 DEG C of baking 10h, last gained black solid under -0.1MPa
Material is product sulfonic acid carbon nano tube/graphene oxide composite catalyst.
Step（1）Middle sodium p styrene sulfonate purity is 90%-99.99%.
Using the mixed fine filter membrane of water system, pore size is 0.30-0.50 μm.
The application of the sulfonic acid carbon nano tube/graphene oxide composite catalyst：For Long carbon chain carboxylic acid and fatty alcohol
Esterification, be the dehydration of Long carbon chain carboxylic acid and fatty alcohol, reaction equation is as follows：
R1For the alkyl of carbon atom >=10, including double bond alkyl, phenyl ring and substituted benzene ring；R2For the alkane of carbon number >=8
Base and hydroxyl are in end position.
By obtained sulfonic acid carbon nano tube/graphene oxide composite catalyst be used for higher fatty acids laurate with it is different pungent
In the reaction of alcohol.Concretely comprise the following steps：4g laurate, 10mL isooctanol are added in 25mL three-necked flasks, 2wt % are added sulfonated
CNT/graphene oxide composite catalyst, 90 DEG C of reaction 6h of normal pressure, is sampled every 0.5h and observed, dripped using standard acid-base
The method of determining determines the change of its reaction yield, is finally proved with gas-chromatography, measures esterification yied.
Beneficial effects of the present invention：The present invention uses sulfonic acid group as catalytic reaction activity center, immobilized in big
On the carrier of specific surface area, pollution of the monomer sulfonic acid class catalyst for environment can be substantially reduced；Prepared catalyst be used for liquid-
It is easy to separation after solid phase reaction, reaction, and factory cost can be substantially reduced with recycled for multiple times；Received using new carbon
Mitron/graphene oxide increases substantially the catalytic efficiency of catalyst as the carrier of catalyst, and compare other same type sulphurs
Acids esterification catalyst, with higher esterification yied and reaction selectivity.Sulfonic acid carbon nano tube/oxygen prepared by the present invention
Graphite alkene composite catalyst, available for the esterification of Long carbon chain carboxylic acid and fatty alcohol, and reaction yield is higher, solves work
The Long carbon chain carboxylic acid relatively low technical barrier of yield in the esterification reaction in industry production.
Brief description of the drawings
Fig. 1 is to change over time curve map using laurate during different catalysts and isooctanol yield.
Embodiment
With reference to some examples and accompanying drawing, the present invention will be further described, but the interest field of the present invention is not limited only to
The scope of example.
Embodiment 1
1g sodium p styrene sulfonates are taken to be dissolved in 100mL distilled water, addition 50mg multi-walled carbon nanotubes, 50KHz ultrasound 1h,
300-500rpm stirs 3h；Mixture after stirring is moved into three-necked flask, 0.5g potassium peroxydisulfates, and maintaining nitrogen purge is added
30min, removes the oxygen in reaction system；Then three-necked flask is put into oil bath pan, 90 DEG C, 500- are to slowly warm up to
800rpm uniform stirrings 4h；After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Then will filtering gained
Solid matter is added in 50mL 35%-37.5% concentrated hydrochloric acid, the condensing reflux 8h at 80 DEG C；Solution is filtered again, finally used
Deionized water is washed 5 times, solid is dried in vacuo, gained atrament is sulfonated modified carbon nano-tube.Take sulfonated change
Property CNT 40mg mixed with 40mg graphene oxides, add 100mL ethanol, be placed in 250mL three-necked flasks, 50KHz surpass
Sound 30min, 100 DEG C are heated to reflux 2h；After backflow terminates, by solution with mixed fine membrane filtration, it is washed with deionized 5 times, will
Solid is dried in vacuo, and finally gives sulfonic acid carbon nano tube/graphene oxide composite catalyst.
By obtained sulfonic acid carbon nano tube/graphene oxide composite catalyst be used for higher fatty acids laurate with it is different pungent
In the reaction of alcohol.4g laurate, 10mL isooctanol are added in 25mL three-necked flasks, 2wt % sulfonic acid carbon nano tube/oxygen is added
Graphite alkene composite catalyst, 90 DEG C of reaction 6h of normal pressure, samples every 0.5h and observes, determine its using standard acid-base titrimetric method anti-
Product yield changes, and is finally proved with gas-chromatography, and it is 43.25% to measure esterification yied.Using same procedure, 2wt % are used
Dense H2SO4As catalyst, it is 28.36%, sulfonic acid carbon nano tube/graphite oxide prepared by us finally to measure esterification yied
Alkene composite catalyst is in contrast to traditional dense H2SO4, 0.5 times of yield raising.
Embodiment 2
Take 2g sodium p styrene sulfonates to be dissolved in 100mL distilled water, be subsequently added 50mg multi-walled carbon nanotubes, 50KHz surpasses
Sound 1h, 300-500rpm stirring 3h；Mixture after stirring is moved into three-necked flask, 0.5g potassium peroxydisulfates are added, and continue
Nitrogen 30min is passed through, the oxygen in reaction system is removed；Then three-necked flask is put into oil bath pan, 90 DEG C are to slowly warm up to,
500-800rpm uniform stirrings 4h；After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Then will filtering
Gained solid matter is added in 50mL 35%-37.5% concentrated hydrochloric acid, the condensing reflux 8h at 80 DEG C；Solution is filtered again, most
After be washed with deionized 5 times, solid is dried in vacuo, gained atrament is sulfonated modified carbon nano-tube.Take sulfonic acid
Change modified carbon nano-tube 40mg to mix with 60mg graphene oxides, add 100mL ethanol, be placed in 250mL three-necked flasks,
50KHz ultrasound 30min, 90 DEG C are heated to reflux 2h；After backflow terminates, by solution with mixed fine membrane filtration, 5 are washed with deionized
It is secondary, solid is dried in vacuo, sulfonic acid carbon nano tube/graphene oxide composite catalyst is finally given.
By obtained sulfonic acid carbon nano tube/graphene oxide composite catalyst be used for higher fatty acids laurate with it is different pungent
In the reaction of alcohol.Carried out according to the methods described of embodiment 1, ultimate yield is 49.13% after reaction 6h.It is dense in comparative example 1
H2SO4Yield, improves 0.73 times.
Embodiment 3
Take 5g sodium p styrene sulfonates to be dissolved in 100mL distilled water, be subsequently added 100mg multi-walled carbon nanotubes, 50KHz surpasses
Sound 1h, 300-500rpm stirring 3h；Mixture after stirring is moved into three-necked flask, 0.5g potassium peroxydisulfates are added, and continue
Nitrogen 30min is passed through, the oxygen in reaction system is removed；Then three-necked flask is put into oil bath pan, 90 DEG C are to slowly warm up to,
500-800rpm uniform stirrings 4h；After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5 times.Then will filtering
Gained solid matter is added in 50mL 35%-37.5% concentrated hydrochloric acid, the condensing reflux 8h at 80 DEG C；Solution is filtered again, most
After be washed with deionized 5 times, solid is dried in vacuo, gained atrament is sulfonated modified carbon nano-tube.Take sulfonic acid
Change modified carbon nano-tube 40mg to mix with 60m graphene oxides, add 100mL ethanol, be placed in 250mL three-necked flasks, 50KHz
Ultrasonic 30min, 110 DEG C are heated to reflux 2h；After backflow terminates, by solution with mixed fine membrane filtration, it is washed with deionized 5 times,
Solid is dried in vacuo, sulfonic acid carbon nano tube/graphene oxide composite catalyst is finally given.
By obtained sulfonic acid carbon nano tube/graphene oxide composite catalyst be used for higher fatty acids laurate with it is different pungent
In the reaction of alcohol.Carried out according to the methods described of embodiment 2, ultimate yield is 52.12% after 90 DEG C of reaction 6h of normal pressure.Contrast is implemented
Dense H in example 12SO4Yield, improves 0.84 times.
Embodiment 4
Sulfonic acid carbon nano tube/graphene oxide composite catalyst is prepared according to embodiment 2, is applied to senior fat
In the reaction of fat acid laurate and isooctanol, 4g laurate is added in 25mL three-necked flasks, 10mL isooctanol adds 2wt %
Sulfonic acid carbon nano tube/graphene oxide composite catalyst, normal pressure, reduction reaction temperature is reacted 6h, taken every 0.5h to 60 DEG C
Sample is observed, and is determined the change of its reaction yield using standard acid-base titrimetric method, is finally proved with gas-chromatography, measure final ester
It is 43.94% to change yield.
Embodiment 5
The higher fatty acids laurate of the composite catalyst of the present invention will not be added to enter with isooctanol according to the method for embodiment 2
Row reaction, it is 19.37% to measure blank esterification yied.
Embodiment 6
Commercially available sulphonic acids solid acid esterification catalyst is purchased, the anti-of higher fatty acids laurate and isooctanol is used it for
Should, reacted according to the method for embodiment 2, it is 35.23% to measure ultimate yield.
By embodiment 2, embodiment 6 and dense H2SO4These three different catalysts are contrasted with blank reaction, by laurate
Drawing of Curve is changed over time with isooctanol yield intuitively to be contrasted into Fig. 1.
It can be seen that by the various embodiments described above and Fig. 1, new sulfonic acid carbon nano tube/graphene oxide prepared by the present invention
Composite catalyst contrasts the catalyst that other same type catalyst and markets are sold, and has a clear superiority.Shown in Fig. 1,
React after 1.5h, esterification yied is close to 40%, it is seen that the composite catalyst reactivity prepared by the present invention is higher, is applied to
Can be significantly cost-effective in industrial production, and asepsis environment-protecting, it is a kind of new catalytic for having larger industry to be esterified application prospect
Material.
Claims (5)
1. a kind of preparation method of sulfonic acid carbon nano tube/graphene oxide composite catalyst, it is characterised in that step is：
（1）Take 1-5g sodium p styrene sulfonates to be dissolved in 100mL distilled water, add 20-100mg multi-walled carbon nanotubes, use
50KHz supersonic wave cleaning machine continuous ultrasound 1-2h, then with 300-500rpm rotating speed uniform stirring 3-5h；Will be mixed after stirring
Compound move into three-necked flask in, add 0.2-1g potassium peroxydisulfates, and with bubble type lead to nitrogen method removal system in oxygen, when
Between maintain 30-60min；Reaction system is to slowly warm up to 90 DEG C, with 500-800rpm rotating speed uniform stirring 4-6h；
（2）After reaction terminates, with mixed fine membrane filtration, deionized water centrifuge washing 5-8 times；50mL is added in filtering gained solid
Mass concentration is 35%-37.5% concentrated hydrochloric acid, the condensing reflux 8h at a temperature of 70-100 DEG C；
（3）By step（2）Resulting solution reuses mixed fine membrane filtration, is finally washed with deionized 5-10 times, by gained
Solid matter is placed in vacuum drying chamber, the 50-70 DEG C of baking 10h under -0.1MPa, and gained atrament is sulfonated modification
CNT；
（4）By step（3）Obtained sulfonated modified carbon nano-tube 40mg is mixed with graphene oxide 20-100mg, is added to
In 100mL ethanol, using 50KHz supersonic wave cleaning machine continuous ultrasound 10-30min, then heated back at a temperature of 90-130 DEG C
Flow 1-2h；Backflow terminates rear repeat step（3）Middle step reuses mixed fine membrane filtration, and 5-10 is finally washed with deionized
It is secondary, gained solid matter is placed in vacuum drying chamber, 50-70 DEG C of baking 10h, last gained black solid thing under -0.1MPa
Matter is product sulfonic acid carbon nano tube/graphene oxide composite catalyst.
2. the preparation method of sulfonic acid carbon nano tube/graphene oxide composite catalyst according to claim 1, its feature exists
In：Step（1）Middle sodium p styrene sulfonate purity is 90%-99.99%.
3. the preparation method of sulfonic acid carbon nano tube/graphene oxide composite catalyst according to claim 1, its feature exists
In：Using the mixed fine filter membrane of water system, pore size is 0.30-0.50 μm.
4. the application of the sulfonic acid carbon nano tube/graphene oxide composite catalyst prepared with claim 1 methods described, it is special
Levy and be：It is the dehydration of Long carbon chain carboxylic acid and fatty alcohol for the esterification of Long carbon chain carboxylic acid and fatty alcohol, reaction
Formula is as follows：
R1For the alkyl of carbon atom >=10；R2Position is being held for the alkyl and hydroxyl of carbon number >=8.
5. the application of sulfonic acid carbon nano tube/graphene oxide composite catalyst as claimed in claim 4, it is characterised in that will make
Sulfonic acid carbon nano tube/graphene oxide the composite catalyst obtained is used in the reaction of higher fatty acids laurate and isooctanol,
Concretely comprise the following steps：4g laurate, 10mL isooctanol are added in 25mL three-necked flasks, 2wt % sulfonic acid carbon nano tube/oxygen is added
Graphite alkene composite catalyst, 90 DEG C of reaction 6h of normal pressure, samples every 0.5h and observes, determine its using standard acid-base titrimetric method anti-
Product yield changes, and is finally proved with gas-chromatography, measures esterification yied.
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| CN108251076B (en) * | 2016-12-29 | 2020-03-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof |
| 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 |
| 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 |
| 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 |
| 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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