CN109761737A - Carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation - Google Patents
Carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation Download PDFInfo
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Abstract
The invention belongs to catalyst applied technical fields, the application of alkene is prepared more particularly to carbon nitride material catalysis low-carbon alkanes oxidative dehydrogenation, carbon nitride material is activated under air, oxygen, carbon dioxide, nitrogen dioxide or steam atmosphere and obtains activated carbon nitride material, then activated carbon nitride material is directly applied into low-carbon alkanes oxidative dehydrogenation；Carbonitride preparation cost is low, simple and easy to get, suitable for the industrialized production of low-carbon alkanes oxidative dehydrogenation alkene, has high olefine selective, no carbon distribution, the service life is long, and application prospect is very wide.
Description
Technical field:
The invention belongs to catalyst applied technical fields, and in particular to carbon nitride material is catalyzed low-carbon alkanes oxidative dehydrogenation system
The application of standby alkene.
Background technique:
As the proved reserves of natural gas are continuously increased and the rapid development of production technique, the cost of low-carbon alkanes is substantially
Decline, is catalytically conveted to corresponding alkene and oxygenatedchemicals etc. using low-carbon alkanes resource (C2~C5) abundant in natural gas
Industrial chemicals can greatly alleviate the deficient crisis of industrial chemicals.C h bond is quite stable in low-carbon alkanes, and activation is difficult
Degree is big, and which results in alkane anaerobic dehydrogenation processes to need higher energy, improves production cost, and low-carbon alkanes oxidative dehydrogenation
Process is not limited by thermodynamics, is the method for being most hopeful to replace anaerobic dehydrogenation alkene at present.But the C- in Product olefins
C bond energy is weaker than the C-H in reactant, this is just caused is easy to appear in the reaction process of low-carbon alkanes oxidative dehydrogenation alkene
Deep oxidation product (CO, CO2), to reduce the selectivity of target product olefins.Therefore a kind of efficient catalyst is developed
Still it is a problem to be solved.
The catalyst of low-carbon alkanes oxidative dehydrogenation at present mostly uses metal oxide, but since such catalyst is stronger
Oxidisability, so the yield of alkene is less able to breakthrough 20%.In recent years, researcher finds boron nitride material in low-carbon alkanes
Excellent olefine selective is shown in oxidative dehydrogenation, yield can achieve 20% or more (Grant J T, Carrero C
A,Goeltl F,et al.Selective oxidative dehydrogenation of propane to propene
using boron nitride catalysts[J].Science,2016,354(6319):1570-1573；Venegas J
M,Grant J T,McDermott W P,et al.Selective Oxidation of n-Butane and Isobutane
Catalyzed by Boron Nitride[J].ChemCatChem,2017,9(12):2118-2127；Huang R,Zhang
B,Wang J,et al.Direct Insight into Ethane Oxidative Dehydrogenation over
Boron Nitrides[J].ChemCatChem,2017,9(17):3293-3297).The appearance of nitridation B catalyst greatly pushes away
Low-carbon alkanes oxidative dehydrogenation has been moved to move towards the industrialization, but since boron nitride material preparation process is complicated, higher cost.Therefore it opens
It sends out the excellent cheap catalyst of catalytic performance a kind of and is still a huge challenge.
Summary of the invention:
It is an object of the invention to overcome disadvantage of the existing technology, design proposes carbon nitride material in catalysis lower alkanes
Hydrocarbon oxidative dehydrogenation prepares the application in alkene, preparation process is simple, the carbonitride nonmetallic materials of large scale preparation is facilitated to use
High selectivity and stability are shown in low-carbon alkanes oxidative dehydrogenation such as propane, normal butane, iso-butane and isopentane.
To achieve the above object, carbon nitride material is used to be catalyzed the tool that low-carbon alkanes oxidative dehydrogenation prepares alkene by the present invention
Body process are as follows:
(1) carbon nitride material is lived under air, oxygen, carbon dioxide, nitrogen dioxide or steam atmosphere
The carbon nitride material changed, activation temperature are 200~550 DEG C, and activation time is 6~72h；
(2) when activated carbon nitride material being directly applied to low-carbon alkanes oxidative dehydrogenation, reaction temperature 300
~550 DEG C, wherein preferably 400~550 DEG C of propane, preferably 300~450 DEG C of normal butane, iso-butane, pentane preferably 300~450
DEG C, the volume ratio of reactant and oxidant is (1~8): 1, preferably (3~5): 1.
Oxidant in low-carbon alkanes oxidative dehydrogenation of the present invention is oxygen, air, carbon dioxide, an oxidation
Carbon, carbon dioxide, carbon monoxide or vapor, preferably air or oxygen；It can be used inert gas as diluent in reaction,
Diluent can not used.
Inert gas of the present invention is helium, nitrogen or argon gas, preferably nitrogen.
The operation principle of the present invention is that: after being oxidized agent activation, sawtooth position occurs oxidation reaction and generates carbonitride
Carbonyl, carbonyl are reacted with hydrogen in low-carbon alkanes at a certain temperature, become hydroxyl, so that the hydrogen taken off in low-carbon alkanes obtains phase
Corresponding alkene, since there is carbonitride stable two-dimensional structure to improve in product while guaranteeing material thermal stability
The selectivity of alkene.
For the present invention compared with commercialized boron nitride in the prior art, carbonitride reaches similar olefine selective,
But the cost of carbon nitride catalyst is lower, and compared with traditional vanadium catalyst, under similar alkane conversion, the selection of alkene
Property improve nearly 10%；In 48 hours steady testings, the catalytic activity of carbonitride is almost unchanged, and the yield of alkene is even more to reach
20%；Importantly, the overall selectivity of alkene is even more to reach 90% or so when alkane conversion is lower than 10%；Nitridation
Carbon preparation cost is low, simple and easy to get, suitable for the industrialized production of low-carbon alkanes oxidative dehydrogenation alkene, has high alkene
Selectivity, no carbon distribution, the service life is long, and application prospect is very wide.
Detailed description of the invention:
Fig. 1 is alkene selection of the carbonitride of the present invention in oxidative dehydrogenation of propane reaction under the conditions of differentiated yields
Property.
Fig. 2 is that carbonitride of the present invention, boron nitride and silicon dioxide carried vanadium are close in oxidative dehydrogenation of propane reaction
Like the selectivity of product comparison under conversion conditions.
Fig. 3 is stability of the carbonitride of the present invention in oxidative dehydrogenation of propane.
Specific embodiment:
The present invention will be further described by way of example and in conjunction with the accompanying drawings, but not limited to this.
Instrument described in the present embodiment unless otherwise specified, commercially obtains.
In the present embodiment, the calculation method of conversion ratio and selectivity is as follows:
Alkane conversion (%)=[(alkane molal quantity after alkane molal quantity-reaction before reacting)/alkane mole before reacting
Number] × 100%
Selectivity of product (%)=[containing carbon number/(alkane carbon number after alkane carbon number-reaction before reacting) in product] × 100%
Product yield (%)=alkane conversion (%) × selectivity of product (%)
Embodiment 1:
The present embodiment carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation, including step is such as
Under:
1) 1.0g carbon nitride material is placed in the quartz ampoule in fixed bed reactors, under the protection of air with 1 DEG C/
Min is warming up to 450 DEG C；
2) after the temperature in step 1) is stablized, it is passed through material mixed gas, wherein the volume ratio of propane and air is 2:1,
The overall flow rate of material mixed gas is 20ml/min, and reaction temperature is 450 DEG C, pressure 0.1MPa, after stablizing half an hour, is started
Acquisition data are simultaneously tested, and test result shows that the conversion ratio of propane is 3.1%, the selectivity 87% of propylene.
Embodiment 2:
The present embodiment carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation, including step is such as
Under:
1) 1.5g carbon nitride material is placed in the quartz ampoule in fixed bed reactors, under the protection of air with 2 DEG C/
Min is warming up to 500 DEG C；
2) after the temperature in step 1) is stablized, it is passed through material mixed gas, wherein the volume ratio of propane and air is 2:1, former
The overall flow rate for expecting gaseous mixture is 30ml/min, and reaction temperature is 500 DEG C, pressure 0.1MPa, after stablizing half an hour, starts to adopt
Collection data are simultaneously tested, and test result shows that the conversion ratio of propane is 13%, the selectivity 76% of propylene.
Embodiment 3:
The present embodiment carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation, including step is such as
Under:
1) 0.7g carbon nitride material is placed in the quartz ampoule in fixed bed reactors, under the protection of air with 5 DEG C/
Min is warming up to 460 DEG C；
2) after the temperature in step 1) is stablized, it is passed through material mixed gas, wherein the volume ratio of propane, oxygen and helium is 4:
1:4, for helium as diluent, the overall flow rate of material mixed gas is 18ml/min, and reaction temperature is 460 DEG C, pressure 0.1MPa,
After stablizing half an hour, every data of 10 DEG C of acquisitions, and then the variation of conversion of propane and selectivity of product is observed, test
As a result as shown in Figure 1.
Embodiment 4:
The present embodiment selects boron nitride comparison carbon nitride catalyst selectivity, the specific steps are as follows:
Commercially available boron nitride (Sigma Reagent Company) 1.0g is weighed, then the repeatedly step in embodiment 3, acquires propane
The variation of conversion ratio and selectivity of product is chosen similar conversion of propane data and is compared, and test results are shown in figure 2.
Embodiment 5:
The present embodiment chooses vanadium catalyst comparison carbon nitride catalyst selectivity, the specific steps are as follows:
1) in commercially available high-specific surface area SiO2Ammonium metavanadate is directly loaded on material, then in air atmosphere, 500 DEG C
Processing three hours obtains V/SiO2Catalyst；
2) V/SiO prepared in step 1) is weighed2Catalyst 0.5g, then the repeatedly step in embodiment 3, acquires propane
The variation of conversion ratio and selectivity of product is chosen similar conversion of propane data and is compared, and test results are shown in figure 2.
Embodiment 6:
The present embodiment carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation, including step is such as
Under:
1) 1.0g carbon nitride material is placed in the quartz ampoule in fixed bed reactors, under the protection of air with 5 DEG C/
Min is warming up to 500 DEG C；
2) after the temperature in step 1) is stablized, it is passed through material mixed gas, wherein the volume ratio of propane, oxygen and helium is 4:
1:4, for helium as diluent, the overall flow rate of unstripped gas is 27ml/min, and reaction temperature is 500 DEG C, pressure 0.1MPa, is stablized
After half an hour, a data, continuous acquisition 48h are acquired every 2h, and then observe the stability of catalyst catalytic performance, test
As a result as shown in Figure 3.
Claims (3)
1. a kind of carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation, it is characterised in that by carbonitride
Material is for being catalyzed the detailed process that low-carbon alkanes oxidative dehydrogenation prepares alkene are as follows:
(1) carbon nitride material is activated under air, oxygen, carbon dioxide, nitrogen dioxide or steam atmosphere and obtains activating
Carbon nitride material, activation temperature be 200~550 DEG C, activation time be 6~72h；
(2) activated carbon nitride material is directly applied into low-carbon alkanes oxidative dehydrogenation, reaction temperature is 300~550
DEG C, wherein propane is 400~550 DEG C, and normal butane, iso-butane are 300~450 DEG C, and pentane is 300~450 DEG C, reactant and oxygen
The volume ratio of agent is (1~8): 1.
2. carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation according to claim 1, special
Levying the oxidant being in the low-carbon alkanes oxidative dehydrogenation is oxygen, air, carbon dioxide, carbon monoxide, titanium dioxide
Carbon, carbon monoxide or vapor；It can be used inert gas as diluent in reaction, diluent can also not used.
3. carbon nitride material prepares the application in alkene in catalysis low-carbon alkanes oxidative dehydrogenation according to claim 2, special
Sign is that the inert gas is helium, nitrogen or argon gas.
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Cited By (3)
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| CN110743593A (en) * | 2019-10-31 | 2020-02-04 | 中国石油大学(华东) | Application of boron-carbon-nitrogen material in catalyzing oxidative dehydrogenation of low-carbon alkane to prepare olefin |
| CN111111726A (en) * | 2019-11-20 | 2020-05-08 | 北京交通大学 | Preparation method and application of catalyst for preparing propylene by oxidative dehydrogenation of propane |
| CN112973761A (en) * | 2021-03-18 | 2021-06-18 | 宁夏大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
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| CN110743593A (en) * | 2019-10-31 | 2020-02-04 | 中国石油大学(华东) | Application of boron-carbon-nitrogen material in catalyzing oxidative dehydrogenation of low-carbon alkane to prepare olefin |
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| CN112973761A (en) * | 2021-03-18 | 2021-06-18 | 宁夏大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
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