CN109622011A - A kind of amino multi-wall carbon nanotube supported ruthenium catalyst and its preparation and application - Google Patents
A kind of amino multi-wall carbon nanotube supported ruthenium catalyst and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of carbon multi-wall nano tube loaded ruthenium catalyst, and preparation method thereof and its in sugared catalytic hydrogenation prepare the application in sugar alcohol.Multi-walled carbon nanotube through strong acid treatment and ethylenediamine functionalization, is prepared amidized multi-walled carbon nanotube (MWCNTs-NH by the present invention2), and loaded to metal Ru (Ru) in amino multi-wall carbon nanotube by immersion reduction method, prepare the amino multi-wall carbon nanotube load ruthenium (Ru/MWCNTs-NH of high degree of dispersion2) catalyst.Multi-walled carbon nanotube can effectively improve the hydrophilicity on its surface after amino modified, improve the load efficiency and degree of scatter of metal Ru, increase the stability of catalyst.The catalyst can be realized the highly selective preparation of maltitol with optimal conditions, have many advantages, such as that catalytic reaction is high-efficient, product purity is high.In short, catalyst activity metal dispersity of the invention is high, catalytic activity is high, stability is high, preparation process is easy, is conducive to promote.
Description
(1) technical field
The present invention relates to a kind of amino multi-wall carbon nanotube supported ruthenium catalyst, and preparation method thereof and its in maltose
Catalytic hydrogenation prepares the application in sugar alcohol.
(2) background technique
Maltitol is a kind of new type functional sugar alcohol sweetener.Compared with other sugar alcohols, maltitol does not have reproducibility
End, thermal stability and chemical stability are good, under the high temperature conditions long-time heating, Maillard reaction will not occur, for eating
Product production will not change colour；It is not easy to be utilized by microorganism in oral cavity, can be used as the additive of anti-caries；Do not pass through insulin in vivo
Metabolism, does not influence blood glucose, can be used as the nutritive sweetener and auxiliary therapeutical agent of diabetes patient.The application neck of maltitol in recent years
Domain constantly extends, and market prospects are very wide.
Mainly under high temperature, condition of high voltage prepared by hydrogenating reduction by maltose for maltitol.Currently, being used for maltose
Add the catalyst of hydrogen mainly to have a Raney's nickel and loaded noble metal catalyst, however Raney's nickel catalyst there are table catalytic activity compared with
The disadvantages of low, easy inactivation, severe reaction conditions；Loaded catalyst often selects the good noble ruthenium of Hydrogenation as work
Property center, using metal oxide as carrier, but since carrier property is bad, leading to loaded noble metal catalyst, there are metals
The problems such as dispersion degree is not high, stability is poor, so that the purity for the maltitol produced is not high, quality is bad.Therefore, it makes
The new catalyst that standby catalytic activity is high, performance is stable, is of great significance the production of maltitol.
Patent CN106732566A discloses a kind of multi-walled carbon nanotube outer wall load gold using immersion reduction method preparation
The catalyst for belonging to ruthenium nano particle obtains that multi-walled carbon nanotube is intracavitary to be filled with and further to the catalyst high-temperature process
The catalyst of metal ruthenium nano particle.Preparation process needs keep the temperature 3-9h under 350-450 DEG C of hot conditions, energy consumption compared with
Greatly, higher cost, and degree of scatter of the metal Ru in multi-wall carbon nano-tube pipe outer wall or official jargon not can be effectively controlled.
Patent CN101024181A discloses a kind of loaded catalyst prepared using chemical reduction method and electroless plating method,
Porous carrier used by the catalyst there are mechanical strengths it is not high, pore-size distribution is uneven the disadvantages of, catalysis hydrogenation of maltose
During, for the conversion ratio of maltose between 56-97%, catalytic efficiency is not high, and is selectively still not clear.Secondly,
The catalyst uses potassium borohydride reduction agent price higher during the preparation process, causes the preparation cost of catalyst higher.
In conclusion being currently used in catalyst there is the preparation costs higher, catalytic activity of maltitol production technology
The problems such as low, selective bad, stability is poor.
(3) summary of the invention
It is simple, efficient that it is an object of the present invention to provide a kind of preparation process, and catalytic activity is high, stability is good, conducive to recycling
Amino multi-wall carbon nanotube supported ruthenium catalyst, and preparation method thereof and its in maltose catalytic hydrogenation prepare answering in sugar alcohol
With.
The technical solution adopted by the present invention is that:
A kind of amino multi-wall carbon nanotube supported ruthenium catalyst, prepares by the following method:
(1) by multi-walled carbon nanotube, 110~120 DEG C of constant temperature flow back 12~18h in the mixed acid of the concentrated sulfuric acid and concentrated nitric acid,
It filters after the reaction was completed, is washed with distilled water to filtrate and is in neutrality and dries, obtain functionalized multi-wall carbonnanotubes, further will
The multi-walled carbon nanotube of carboxylated handles 12~18h in ethylenediamine and condensing agent, and after ultrasound filtration removes impurity, drying is obtained
Amino multi-wall carbon nanotube；
(2) it takes amino multi-wall carbon nanotube to be added in ultrapure water, ruthenium trichloride, ethylene glycol is added, is warming up to 80~90
DEG C, after being stirred at reflux 12~18h, solution after reaction is filtered, is washed with distilled water catalyst to neutrality, in 60~70 DEG C of conditions
The amino multi-wall carbon nanotube supported ruthenium catalyst, i.e. Ru/MWCNTs-NH is made in lower vacuum drying2Catalyst.
The multi-walled carbon nanotube size are as follows: 5~10nm of mean inside diameter, 20~40nm of outer diameter, 10~30 μm of length.
The invention further relates to the methods for preparing the carbon multi-wall nano tube loaded ruthenium catalyst, which comprises
(1) 120 DEG C of constant temperature reflux in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid volume ratio 3:1 by multi-walled carbon nanotube
12h is filtered after the reaction was completed, is washed with distilled water to filtrate and is in neutrality, and in 60 DEG C of vacuum drying 12h, obtains function carboxylated
Multi-walled carbon nanotube；
(2) multi-walled carbon nanotube of function carboxylated, ethylenediamine and dicyclohexylcarbodiimide condensing agent are added separately to
In single necked round bottom flask, it is uniformly mixed, flow back 12h at 120 DEG C, after the reaction was completed, with anhydrous second under the conditions of supersonic oscillations
Alcohol washes away extra amine, DCC and other by-products, is filtered with 0.22 μm of the PTFE filter membrane in aperture, by filter cake in 60 DEG C of vacuum
Under the conditions of dry 12h, obtain amino multi-wall carbon nanotube；
(3) it takes amino multi-wall carbon nanotube to be added in ultrapure water, ruthenium trichloride, ethylene glycol is added, is warming up to 80 DEG C, stirs
After mixing reflux 12h, solution after reaction is filtered, catalyst is washed with distilled water to neutrality, is dried in vacuo under the conditions of 60 DEG C
The amino multi-wall carbon nanotube supported ruthenium catalyst, i.e. Ru/MWCNTs-NH is made in 12h2Catalyst.
The invention further relates to the amino multi-wall carbon nanotube supported ruthenium catalysts to prepare sugar in maltose catalytic hydrogenation
Application in alcohol.
The application are as follows: prepare the maltose solution of mass concentration 5~20%, be added in reaction kettle, addition quality is wheat
The Ru/MWCNTs-NH of bud saccharic amount 5~10%2Catalyst seals reaction kettle, displaces air in reaction kettle with nitrogen, sets
Temperature of reaction kettle is 100~140 DEG C, 300~700rpm of speed of agitator, and after temperature is stablized, being filled with air pressure in hydrogen to kettle is 3.0
~4.0MPa, after reacting 60~100min, cooling reaction kettle when temperature drops to room temperature, releases hydrogen, reaction was completed.
Reaction product is diluted 50 times with ultrapure water, is tested and analyzed using high performance liquid chromatography, main measurement is anti-
Substrate sugar residual quantity in liquid, the content of product sugar alcohol are answered, the conversion ratio of substrate and the selectivity of product are analyzed, in this, as catalysis
The active evaluation criterion of agent.
After reaction, catalyst recycling can be recycled, the catalyst recovery method is as follows: last batch reaction produces
Object 8000rpm be centrifuged 10min, abandon supernatant, with ultrapure water centrifuge washing three times after, vacuum drying under the conditions of 60 DEG C, after drying
Ru/MWCNTs-NH2Hydrogenation of maltose of the catalyst for next batch reacts.
The beneficial effects are mainly reflected as follows: the present invention provides a kind of amino multi-wall carbon nanotube load rutheniums to urge
Amino is introduced into high mechanical strength by agent and preparation method thereof and its application in maltitol production, the present invention
Multi-wall carbon nano-tube pipe surface improves the hydrophilicity on its surface, improves the load efficiency of metal Ru particle, and metal Ru
The load capacity of grain is high, good dispersion.The catalyst can be realized the high conversion and maltitol of maltose with optimal conditions
It is highly selective, and the reaction time is short, catalyst amount is small；Secondly, the stability of the catalyst is good, it is conducive to recycling, and
It may be implemented to repeatedly use, catalyst cost is greatly reduced.It reuses to the 8th batch, the conversion ratio of maltose exists
94% or more, the selectivity of maltitol is 93% or more.
(4) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Embodiment 1:Ru/MWCNTs-NH2The preparation of catalyst
(1) multi-walled carbon nanotube (mean inside diameter 5-10nm, outer diameter 20- the preparation of functionalized multi-wall carbonnanotubes: are weighed
40nm, 10-30 μm of length) 5.0 grams be placed in the round-bottomed flask of 250mL, the concentrated sulfuric acid and concentrated nitric acid (volume ratio 3:1) mixing is added
Solution 100mL, loads onto reflux condensing tube, with oil bath heating to 120 DEG C, constant temperature reflux 12h under stirring condition, and cooled and filtered,
To distill water washing to filtrate pH value for neutrality, then 60 DEG C of dry 12h, the multi wall carbon for obtaining carboxylated are received in vacuum drying oven
Mitron (MWCNTs-COOH).
(2) preparation of amino multi-wall carbon nanotube: MWCNTs-COOH, 50mL ethylenediamine and 8g that step (1) is obtained
Dicyclohexylcarbodiimide (DCC) condensing agent is added separately in 250mL single necked round bottom flask, is uniformly mixed, is flowed back at 120 DEG C
12h.After the reaction was completed, extra amine, DCC and other by-products are washed away with dehydrated alcohol under the conditions of supersonic oscillations.With
Filter cake is dried under 60 DEG C of vacuum conditions 12h, obtains amination multi-wall carbon nano-tube by PTFE filter membrane (0.22 μm of aperture) filtering
Pipe.
(3) immersion reduction method prepares Ru/MWCNTs-NH2: weighing 1.0g amino multi-wall carbon nanotube, to be added to 100mL super
In pure water, 0.16g ruthenium trichloride is added, 20mL ethylene glycol is added, is warming up to 80 DEG C, is stirred at reflux 12h.It is molten after precipitating is complete
Liquid heat filtering is washed with distilled water catalyst to neutrality.Filter cake dry 12h under 60 DEG C of vacuum conditions, being made, there is catalysis to live
The Ru/MWCNTs-NH of property2Catalyst, wherein wherein the partial size of Ru is between 1.8~4.5nm, average grain diameter 3.1nm, Ru
Load capacity be 6%.
Embodiment 2: the conversion ratio of maltose and the selective enumeration method method of maltitol
The reactant before sealing reaction kettle and the 20 μ L of product after hydrogenation reaction are taken respectively, are diluted to 1mL with ultrapure water,
The concentration of maltose in reactant is detected by high performance liquid chromatography, the residual concentration of maltose and maltose are pure and strong in product
Degree.
Detecting high performance liquid chromatograph device used is 2414 Composition distribution of waters system, chromatographic column Aminex
HPX-87H column (300 × 7.8mm), mobile phase 5mM H2SO4, flow velocity 0.6mL/min, column temperature: 60.0 DEG C, sampling volume: 20 μ L.
The conversion ratio of maltose, the selectivity of maltitol and maltose yield calculation formula are as follows:
Maltitol yield=maltose conversion ratio × maltitol selectivity
Embodiment 3: catalyst activity test
Anhydrous maltose 5.0g is weighed, is added in 45mL ultrapure water, the maltose solution that configuration quality score is 10% will
Maltose solution is transferred in 100mL reaction kettle, and Ru/MWCNTs-NH is added2Catalyst 0.4g seals reaction kettle.It will with nitrogen
Reaction kettle is replaced three times, and air in reaction kettle is excluded.Adjusting temperature of reaction kettle is 120 DEG C, speed of agitator 500rpm, to temperature
After stabilization, hydrogen is filled with to 4.0MPa, starts to react.After reacting 60min, start to be quickly cooled down reaction kettle, when temperature drops to room
Wen Shi is vented hydrogen, terminates hydrogenation reaction.
It is detected using the method for embodiment 2, the conversion ratio of maltose is 78.2%, and the selectivity of maltitol is
89.2%.
Embodiment 4: hydrogenation technique it is time-optimized
Anhydrous maltose 5.0g is weighed, is added in 45mL ultrapure water, the maltose solution that configuration quality score is 10% will
Maltose solution is transferred in 100mL reaction kettle, and Ru/MWCNTs-NH is added2Catalyst 0.4g seals reaction kettle.It will with nitrogen
Reaction kettle is replaced three times, and air in reaction kettle is excluded.Adjusting temperature of reaction kettle is 120 DEG C, speed of agitator 500rpm, to temperature
After stabilization, hydrogen is filled with to 4.0MPa, starts to react.Reaction was completed after 60,70,80,90,100min respectively, is quickly cooled down
Reaction kettle is vented hydrogen when temperature drops to room temperature.
It is detected using the method for embodiment 2, maltose conversion ratio, maltitol selectivity under the differential responses time
And the results are shown in Table 1 for maltitol yield, preferred reaction time 90min.
Table 1: 4 result summary sheet of embodiment
Embodiment 5: the temperature optimization of hydrogenation technique
Anhydrous maltose 5.0g is weighed, is added in 45mL ultrapure water, the maltose solution that configuration quality score is 10% will
Maltose solution is transferred in 100mL reaction kettle, and Ru/MWCNTs-NH is added2Catalyst 0.4g seals reaction kettle.It will with nitrogen
Reaction kettle is replaced three times, and air in reaction kettle is excluded.Adjusting separately temperature of reaction kettle is 60,80,100,120,140 DEG C, stirring
Revolving speed is 500rpm, after temperature is stablized, is filled with hydrogen to 4.0MPa, starts to react.After reacting 90min, start to be quickly cooled down
Reaction kettle is vented hydrogen when temperature drops to room temperature, terminates hydrogenation reaction.
It is detected using the method for embodiment 2, maltose conversion ratio, maltitol selectivity at a temperature of differential responses
And the results are shown in Table 2 for maltitol yield, preferable reaction temperature is 120 DEG C.
Table 2: 5 result summary sheet of embodiment
Embodiment 6: the rotational speed optimization of hydrogenation technique
Anhydrous maltose 5.0g is weighed, is added in 45mL ultrapure water, the maltose solution that configuration quality score is 10% will
Maltose solution is transferred in 100mL reaction kettle, and Ru/MWCNTs-NH is added2Catalyst 0.4g seals reaction kettle.It will with nitrogen
Reaction kettle is replaced three times, and air in reaction kettle is excluded.Adjust temperature of reaction kettle be 120 DEG C, adjust separately speed of agitator be 300,
400,500,600,700rpm are filled with hydrogen to 4.0MPa, start to react after temperature is stablized.After reacting 90min, start fast
But reaction kettle is vented hydrogen when temperature drops to room temperature to quickly cooling, terminates hydrogenation reaction.
Detected using the method for embodiment 2, maltose conversion ratio under different rotating speeds, maltitol selectivity and
The results are shown in Table 3 for maltitol yield, and preferably speed of agitator is 500rpm.
Table 3: 6 result summary sheet of embodiment
Embodiment 7: the recycling of catalyst
According to the method for embodiment 3, after reacting 90min, hydrogenation reaction is completed.Reaction product is imported into 50mL centrifuge tube
In, 8000rpm is centrifuged 10min, and 20 μ L supernatants is taken to carry out liquid chromatographic detection, and the conversion ratio for obtaining maltose is 100%, wheat
The selectivity of bud sugar alcohol is 99.3%.Remaining supernatant in centrifuge tube is discarded, after ultrapure water will precipitate centrifuge washing, in 60 DEG C of items
Vacuum drying under part.Ru/MWCNTs-NH after drying2Hydrogenation of maltose of the catalyst for next batch reacts.Repetitive operation
After 8 times, the conversion ratio of maltose is 94% or more, and the selectivity of maltitol is 93% or more.Different batches hydrogenation reaction
Maltose conversion ratio and maltitol are selectively as shown in table 4.
Table 4: the Ru/MWCNTs-NH of different batches2It is catalyzed hydrogenation of maltose sugared conversion ratio and sugar alcohol selectivity in the process
Claims (6)
1. a kind of amino multi-wall carbon nanotube supported ruthenium catalyst, prepares by the following method:
(1) 110~120 DEG C of constant temperature 12~18h of reflux, reaction in the mixed acid of the concentrated sulfuric acid and concentrated nitric acid by multi-walled carbon nanotube
It filters after the completion, is washed with distilled water to filtrate and is in neutrality and dries, obtain functionalized multi-wall carbonnanotubes, further by carboxyl
The multi-walled carbon nanotube of change handles 12~18h in ethylenediamine and condensing agent, and after ultrasound filtration removes impurity, drying obtains amino
Multi-walled carbon nano-tube；
(2) it takes amino multi-wall carbon nanotube to be added in ultrapure water, ruthenium trichloride, ethylene glycol is added, is warming up to 80~90 DEG C, stirs
After mixing 12~18h of reflux, solution after reaction is filtered, is washed with distilled water catalyst to neutrality, it is true under the conditions of 60~70 DEG C
Sky drying, is made the amino multi-wall carbon nanotube supported ruthenium catalyst, i.e. Ru/MWCNTs-NH2Catalyst.
2. carbon multi-wall nano tube loaded ruthenium catalyst as described in claim 1, it is characterised in that the multi-walled carbon nanotube ruler
It is very little are as follows: 5~10nm of mean inside diameter, 20~40nm of outer diameter, 10~30 μm of length.
3. the method for preparing carbon multi-wall nano tube loaded ruthenium catalyst described in claim 1, which comprises
(1) by multi-walled carbon nanotube, 120 DEG C of constant temperature flow back 12h in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid volume ratio 3:1, instead
It should filter after the completion, be washed with distilled water to filtrate and be in neutrality, in 60 DEG C of vacuum drying 12h, obtain the multi wall carbon of function carboxylated
Nanotube；
(2) multi-walled carbon nanotube of function carboxylated, ethylenediamine and dicyclohexylcarbodiimide condensing agent are added separately to single port
In round-bottomed flask, it is uniformly mixed, flow back 12h at 120 DEG C, after the reaction was completed, is washed under the conditions of supersonic oscillations with dehydrated alcohol
Extra amine, DCC and other by-products are removed, are filtered with 0.22 μm of the PTFE filter membrane in aperture, by filter cake in 60 DEG C of vacuum conditions
Lower dry 12h, obtains amino multi-wall carbon nanotube；
(3) it takes amino multi-wall carbon nanotube to be added in ultrapure water, ruthenium trichloride, ethylene glycol is added, is warming up to 80 DEG C, stirs back
After flowing 12h, solution after reaction is filtered, catalyst is washed with distilled water to neutrality, is dried in vacuo 12h under the conditions of 60 DEG C, makes
Obtain the amino multi-wall carbon nanotube supported ruthenium catalyst, i.e. Ru/MWCNTs-NH2Catalyst.
4. carbon multi-wall nano tube loaded ruthenium catalyst of any of claims 1 or 2 is prepared in sugar alcohol in maltose catalytic hydrogenation
Using.
5. application as claimed in claim 4, it is characterised in that the application are as follows: prepare the maltose of mass concentration 5~20%
Solution is added in reaction kettle, and the Ru/MWCNTs-NH that quality is maltose quality 5~10% is added2Catalyst, sealing reaction
Kettle displaces air in reaction kettle with nitrogen, sets temperature of reaction kettle as 100~140 DEG C, 300~700rpm of speed of agitator, temperature
After degree is stablized, being filled with air pressure in hydrogen to kettle is 3.0~4.0MPa, and after reacting 60~100min, cooling reaction kettle, temperature is dropped to
When room temperature, hydrogen is released, reaction was completed.
6. application as claimed in claim 5, it is characterised in that after reaction, recycling catalyst recycling, the catalysis
Agent recovery method is as follows: reaction product 8000rpm be centrifuged 10min, abandon supernatant, with ultrapure water centrifuge washing three times after, at 60 DEG C
Under the conditions of vacuum drying, the Ru/MWCNTs-NH after drying2Hydrogenation of maltose of the catalyst for next batch reacts.
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| CN110586092A (en) * | 2019-10-08 | 2019-12-20 | 烟台大学 | High-dispersion nano-gold catalyst with high activity and good stability and preparation method thereof |
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Application publication date: 20190416 |