CN109304196B - Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method - Google Patents
Heteroatom-containing carbon material, preparation method and application thereof, and hydrocarbon oxidative dehydrogenation method Download PDFInfo
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Abstract
The invention discloses a heteroatom-containing carbon material, a preparation method and application thereof, and a hydrocarbon oxidative dehydrogenation method, wherein the heteroatom-containing carbon material contains oxygen, nitrogen, hydrogen and carbon, in an X-ray diffraction pattern of the heteroatom-containing carbon material, dispersion peaks respectively exist between 20-30 degrees and 40-50 degrees of a 2 theta angle, the content of surface oxygen determined by an X-ray photoelectron spectrum is a, the content of bulk oxygen determined by an element analysis method is b, and a/b is more than or equal to 2. The carbon material containing hetero atoms is used as catalyst for hydrocarbon oxidizing and dehydrogenating reaction, and can obtain obviously raised olefin selectivity, reduce the amount of ineffective burning material and raise the material utilization rate and reaction safety. Also, the heteroatom-containing carbon material according to the present invention is low in cost and easily available.
Description
Technical Field
The invention relates to a carbon material containing heteroatoms, a preparation method and application thereof, and also relates to a hydrocarbon oxidative dehydrogenation method using the carbon material containing heteroatoms as a catalyst.
Background
Carbon materials exist in various morphological structures including carbon nanotubes, graphite, graphene, nanodiamonds, activated carbon, onion carbon, and the like. Compared with the traditional metal oxide catalyst, the carbon material has the advantages of environmental friendliness, reproducibility, low energy consumption and the like, and has good heat-conducting property, so that the carbon material is high in energy utilization rate, and is beneficial to reducing the reaction temperature and improving the product selectivity.
At present, various types of carbon materials have been reported for catalytic reactions such as alkane activation and oxidative dehydrogenation. For example, in the sixty-seven decades of the last century, researchers have found that coke is capable of catalyzing alkane oxidative dehydrogenation reactions (Journal of Catalysis,31:444-449, 1973); the literature (ACTA PHYSICA POLONIC A, 118(2010)459-464) reports the conversion of n-butane to butenes and butadiene using activated carbon as a catalyst.
The catalytic activity of the simple carbon material is not high, but the surface structure of the carbon material has strong controllability, so that surface modification can be performed artificially, for example, oxygen and other heteroatom functional groups are doped, the electron density distribution and acid-base property of the surface of the carbon material are regulated, and the catalytic activity of the carbon material is improved. For example, the performance of carbon nanotubes in oxidative dehydrogenation of butane can be greatly improved by phosphorus and nitrogen modification (Catalysis Today,102:248-253, 2005; Science Vol.322(3),73-77,2008).
However, carbon nanotubes are very expensive and not easy to prepare. In addition, the total selectivity of the carbon material obtained by the method reported in the prior art in the alkane oxidative dehydrogenation reaction is difficult to reach more than 60%, that is, nearly more than half of the feed materials in the reaction are subjected to ineffective combustion reaction, and excessive combustion reaction not only reduces the utilization rate of the raw materials, but also reduces the safety of the reaction, so that the carbon material is difficult to be put into practical use in the alkane oxidative dehydrogenation reaction.
Therefore, there is an urgent need to improve the product selectivity of carbon materials in alkane oxidative dehydrogenation reactions, thereby improving the raw material utilization rate and the reaction safety.
Disclosure of Invention
The invention aims to overcome the technical problem that the product selectivity is low when the existing carbon material is used as a catalyst for hydrocarbon oxidative dehydrogenation reaction, and provides a heteroatom-containing carbon material which shows obviously improved product selectivity in the hydrocarbon oxidative dehydrogenation reaction.
According to a first aspect of the present invention, there is provided a heteroatom-containing carbon material containing an oxygen element in an amount of 1 to 10% by weight, a nitrogen element in an amount of 0.01 to 4% by weight, a hydrogen element in an amount of 0.1 to 3% by weight, and a carbon element in an amount of 83 to 98.89% by weight, based on the total amount of the heteroatom-containing carbon material and calculated as the elements,
in an X-ray diffraction pattern of the carbon material containing the heteroatom, dispersion peaks exist respectively at the 2 theta angle of 20-30 degrees and at the 2 theta angle of 40-50 degrees;
in the heteroatom-containing carbon material, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by an elemental analysis method is b, and a/b is more than or equal to 2.
According to a second aspect of the present invention, there is provided a method for producing a heteroatom-containing carbon material, the method comprising: roasting a raw material carbon material at the temperature of 400-1200 ℃ in a reactive atmosphere, wherein the reactive atmosphere contains ammonia gas, optional carrier gas and optional water vapor;
the raw material carbon material contains oxygen element, hydrogen element and carbon element, wherein the content of the oxygen element is 0.2-12 wt%, the content of the hydrogen element is 0.05-3 wt%, and the content of the carbon element is 85-99.75 wt% based on the total amount of the raw material carbon material and calculated by the elements;
in an X-ray diffraction pattern of the raw material carbon material, dispersion peaks exist between 20 degrees and 30 degrees of a 2 theta angle and between 40 degrees and 50 degrees respectively;
in the raw material carbon material, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by an elemental analysis method is b, and a/b is less than 2.
According to a third aspect of the present invention there is provided a heteroatom-containing carbon material produced by the method of the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided the use of a heteroatom-containing carbon material of the first or third aspect of the present invention as a catalyst for the oxidative dehydrogenation of hydrocarbons.
According to a fifth aspect of the present invention there is provided a process for the oxidative dehydrogenation of a hydrocarbon, which process comprises contacting the hydrocarbon with a heteroatom-containing carbon material as described in the first or third aspects of the present invention under oxidative dehydrogenation reaction conditions.
The carbon material containing the heteroatom is used as a catalyst for hydrocarbon oxidative dehydrogenation, so that the olefin selectivity can be obviously improved, the raw material amount of ineffective combustion is reduced, and the raw material utilization rate and the reaction safety are improved. Also, the heteroatom-containing carbon material according to the present invention does not need to use expensive carbon tubes as a raw material, but rather uses a relatively inexpensive amorphous carbon material as a raw material, and thus the heteroatom-containing carbon material according to the present invention is low in cost and is easily available.
Drawings
FIG. 1 is an X-ray diffraction spectrum of the raw material carbon material used in example 1.
FIG. 2 is an X-ray diffraction pattern of the heteroatom-containing carbon material prepared in example 1.
Fig. 3 is an X-ray diffraction pattern of the carbon nanotube used as the raw material in comparative example 1.
Fig. 4 is an X-ray diffraction pattern of the heteroatom-containing carbon nanotube prepared in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a heteroatom-containing carbon material containing an oxygen element, a nitrogen element, a hydrogen element and a carbon element.
The content of the oxygen element in the heteroatom-containing carbon material according to the present invention is 1 to 10% by weight, preferably 1.2 to 8% by weight, more preferably 1.5 to 6% by weight, in terms of element, based on the total amount of the heteroatom-containing carbon material; the content of the nitrogen element is 0.01-4 wt%, preferably 0.03-3 wt%, and more preferably 0.05-2 wt%; the content of the hydrogen element is 0.1 to 3 wt%, preferably 0.2 to 2.5 wt%, and more preferably 0.4 to 2 wt%; the content of the carbon element is 83 to 98.89 wt%, preferably 86.5 to 98.57 wt%, more preferably 90 to 98.05 wt%.
In the present invention, the content of each element in the heteroatom-containing carbon material and the raw material carbon material is measured by an elemental analysis method. In the invention, the elemental analysis is carried out on an element analyzer of Elementar Micro Cube, and the specific operation method and conditions are as follows: weighing 1-2mg of sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (for removing atmospheric interference during sample feeding, helium gas is adopted for blowing), and then reducing the combusted gas by using reduced copper to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and is sequentially detected by a Thermal Conductivity Detector (TCD). The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
According to the heteroatom-containing carbon material of the present invention, in the X-ray diffraction pattern of the heteroatom-containing carbon material, there are dispersion peaks at an angle of 2 θ of 20 ° to 30 ° and at an angle of 40 ° to 50 °, respectively. The heteroatom-containing carbon material according to the present invention generally does not have a dispersion peak at other positions. The heteroatom-containing carbon material according to the present invention does not have a sharp peak corresponding to carbon in the scanning range (5 ° to 70 °) of X-ray diffraction analysis, i.e., the heteroatom-containing carbon material according to the present invention is in an amorphous state.
In the invention, the dispersion peak refers to a diffraction peak with a half-peak width of not less than 3 degrees, and generally, the half-peak width of the dispersion peak is 3-10 degrees; a sharp peak refers to a diffraction peak having a half-value width of less than 3 °. In the invention, the X-ray diffraction analysis is carried out on a Japanese physical D/MAX-2500 type X-ray diffractometer, CuKalpha rays are adopted, the working voltage is 20kV, the tube current is 10mA, and the scanning range is 5-70 degrees. In the present invention, in the X-ray diffraction pattern, the position of the diffraction peak is determined by the 2 θ angle corresponding to the peak of the diffraction peak.
According to the heteroatom-containing carbon material of the present invention, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by elemental analysis is b, and a/b is 2 or more. From the viewpoint of further improving the product selectivity of the heteroatom-containing carbon material when used as a catalyst for oxidative dehydrogenation of hydrocarbons, a/b is preferably 2 to 5, more preferably 2.1 to 4.5.
In the present invention, the X-ray photoelectron spectroscopy was carried out on an ESCALab250 type X-ray photoelectron spectrometer equipped with Thermo Avantage V5.926 software of Thermo Scientific, the excitation source was monochromatized Al Kalpha X-ray, the energy was 1486.6eV, the power was 150W, the transmission energy for narrow scan was 30eV, and the base vacuum during analysis and test was 6.5X 10-10mbar, electron binding energy was corrected for the C1s peak (284.6eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 c and 1 atm under a helium atmosphere for 3 hours before testing.
According to the heteroatom-containing carbon material of the present invention, the specific surface area of the heteroatom-containing carbon material is 100m or more2A ratio of ≥ 500m2G, more preferably ≥ 600m2(ii)/g, more preferably 700-2(ii)/g, for example, can be 750- & ltwbr/& gt1300 m2(ii) in terms of/g. In the present invention, the specific surface area is measured by the nitrogen adsorption BET method.
According to the heteroatom-containing carbon material of the present invention, the heteroatom-containing carbon material is produced using amorphous carbon as a raw material, and the volume average particle diameter thereof may be generally 20 to 850 μm, preferably 50 to 400 μm, and more preferably 60 to 260 μm. In the present invention, the volume average particle diameter is measured by a laser particle size analyzer.
The content of other non-metallic hetero atoms such as sulfur atom and phosphorus atom in the hetero atom-containing carbon material according to the present invention may be a conventional content. Generally, in the heteroatom-containing carbon material according to the present invention, the total amount of non-metallic heteroatoms other than oxygen atoms, hydrogen atoms and nitrogen atoms (such as sulfur atoms and phosphorus atoms) may be 1% by weight or less, preferably 0.5% by weight or less. The heteroatom-containing carbon material according to the present invention may further contain a small amount of metal atoms remaining in the production process of the carbon material, which are usually derived from a catalyst used in the production of the carbon material, and the content of these remaining metal atoms is generally 1% by weight or less, preferably 0.5% by weight or less.
According to a second aspect of the present invention, there is provided a method for producing a heteroatom-containing carbon material, the method comprising: the starting carbon material is calcined in a reactive atmosphere at a temperature of 400-1200 ℃.
According to the method of the second aspect of the present invention, the raw material carbon material contains an oxygen element, a hydrogen element and a carbon element, and the content of the oxygen element is 0.2 to 12% by weight, the content of the hydrogen element is 0.05 to 3% by weight and the content of the carbon element is 85 to 99.75% by weight, based on the total amount of the raw material carbon material and calculated as elements. From the viewpoint of further improving the product selectivity when the finally produced heteroatom-containing carbon material is used as a catalyst for oxidative dehydrogenation of hydrocarbons, the content of the oxygen element is preferably 0.5 to 10% by weight, more preferably 1 to 9.5% by weight, and still more preferably 2 to 9% by weight, in terms of element, based on the total amount of the raw material carbon material; the content of the hydrogen element is preferably 0.1 to 3% by weight, more preferably 0.5 to 2.8% by weight, and further preferably 1 to 2.6% by weight; the content of the carbon element is preferably 87 to 99.4% by weight, more preferably 87.7 to 98.5% by weight, and further preferably 88.4 to 97% by weight.
The total amount (in terms of elements) of the non-metallic hetero atoms other than oxygen atoms and hydrogen atoms (such as sulfur atoms and phosphorus elements) in the raw material carbon material may be a conventional amount. Generally, the total amount of the non-metallic hetero atoms other than oxygen atoms and hydrogen atoms in the raw material carbon material is not more than 1% by weight, preferably not more than 0.5% by weight. According to the method of the present invention, the raw material carbon material may further contain some metal elements, depending on the source, which are generally derived from the catalyst used in the production of the raw material carbon material, in an amount of generally 1% by weight or less, preferably 0.5% by weight or less.
In an X-ray diffraction pattern of the raw material carbon material, dispersion peaks exist between 20 degrees and 30 degrees and between 40 degrees and 50 degrees of a 2 theta angle of the raw material carbon material respectively. According to the method of the second aspect of the invention, the raw material carbon material is generally free from a dispersion peak at other positions. According to the method of the second aspect of the present invention, the raw material carbon material does not have a sharp peak within the scanning range (5 ° to 70 °) of X-ray diffraction analysis, i.e., the raw material carbon material is in an amorphous state, and may be, for example, one or a combination of two or more of activated carbon, coke, charcoal and carbon black, preferably activated carbon.
In the raw material carbon material, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by an elemental analysis method is b, and a/b is less than 2. From the viewpoint of further improving the product selectivity of the finally produced heteroatom-containing carbon material in the hydrocarbon oxidative dehydrogenation reaction, a/b is preferably 0.9 to 1.95, more preferably 1.2 to 1.9.
The specific surface area of the raw material carbon material can be 400-1400m2(ii)/g, preferably 600-2(ii)/g, more preferably 800-2/g。
The volume average particle diameter of the raw material carbon material may be generally 25 to 850. mu.m, preferably 50 to 400. mu.m, and more preferably 80 to 200. mu.m. In the present invention, the volume average particle diameter is measured by a laser particle size analyzer.
According to the method of the second aspect of the present invention, the raw carbon material may be pretreated (e.g., washed) by a method commonly used in the art before use to remove some impurities from the surface of the raw carbon material; the raw material carbon material may be used without pretreatment, and in the embodiment disclosed in the present invention, the raw material carbon material is not pretreated before use.
According to the method of the second aspect of the invention, the reactive atmosphere contains ammonia gas, optionally a carrier gas, and optionally water vapour. The carrier gas may be an inert gas. The inert gas is chemically inert gas, and can be nitrogen and/or a group zero gas, such as one or a combination of two or more of nitrogen, neon, argon and helium.
The amount of ammonia gas is based on the amount of nitrogen atoms that can be introduced into the raw carbon material in sufficient quantities. Generally, the ammonia gas may be present in the reactive atmosphere in an amount of from 0.01 to 5% by volume, preferably from 0.1 to 4% by volume, more preferably from 0.5 to 3% by volume.
According to the method of the second aspect of the present invention, in one embodiment, the reactive atmosphere contains no water vapor, and under the same conditions as the rest of the conditions, the heteroatom-containing nanocarbon material prepared according to this embodiment shows higher olefin selectivity in the oxidative dehydrogenation reaction of hydrocarbons.
According to the method of the second aspect of the present invention, in another embodiment, the reactive atmosphere contains water vapor, and the water vapor is introduced into the reactive atmosphere, under the same conditions as the rest of the conditions, the conversion rate of the raw material of the produced heteroatom-containing nanocarbon material in the oxidative dehydrogenation reaction of hydrocarbon can be further increased. In this embodiment, the content of water vapor in the reactive atmosphere may be 0.01 to 10% by volume, preferably 0.1 to 9% by volume, more preferably 0.2 to 5% by volume, and still more preferably 0.5 to 2% by volume.
According to the method of the second aspect of the present invention, the reactive atmosphere may be a flowing atmosphere or a non-flowing atmosphere, and is not particularly limited. As a flowing atmosphere, the reactive atmosphere may be continuously introduced into the reactor during calcination to displace the atmosphere in the reactor; as a non-flowing atmosphere, the reactive atmosphere is created in the reactor before roasting, and the reactor does not exchange gas with the outside during roasting.
According to the method of the second aspect of the invention, the calcination is carried out at a temperature of 400-1200 ℃, preferably at a temperature of 500-1100 ℃. From the viewpoint of further improving the product selectivity of the finally prepared heteroatom-containing carbon material in the hydrocarbon oxidative dehydrogenation reaction, the calcination is more preferably carried out at a temperature of 700-1000 ℃.
The duration of the firing may be selected according to the temperature at which the firing is carried out. In general, the duration of the calcination may be from 0.5 to 24 hours, preferably from 1 to 8 hours, more preferably from 2 to 6 hours.
According to a third aspect of the present invention there is provided a heteroatom-containing carbon material produced by the method of the second aspect of the present invention.
The carbon material containing the heteroatom or the carbon material containing the heteroatom prepared by the method has good catalytic performance, and obviously improved olefin selectivity is shown in the oxidative dehydrogenation reaction of hydrocarbon substances, so that the utilization rate of raw materials and the yield of products are effectively improved.
The heteroatom-containing carbon material according to the invention or the heteroatom-containing carbon material prepared by the process of the invention can be used as a catalyst either directly or in the form of a shaped catalyst. The shaped catalyst may comprise a heteroatom-containing carbon material according to the invention or a heteroatom-containing carbon material prepared by the process of the invention and a binder. The binder may be selected according to the specific application of the formed catalyst, and may be, for example, an organic binder and/or an inorganic binder, so as to meet the application requirements.
According to a fourth aspect of the present invention there is provided the use of a heteroatom-containing carbon material as described in the first or third aspects of the present invention as a catalyst for the oxidative dehydrogenation of hydrocarbons.
According to the application of the invention, the carbon material containing the heteroatom can be directly used for hydrocarbon oxidative dehydrogenation reaction, and can also be used for hydrocarbon oxidative dehydrogenation reaction after being formed.
According to a fifth aspect of the present invention there is provided a process for the oxidative dehydrogenation of a hydrocarbon, which process comprises contacting the hydrocarbon with a heteroatom-containing carbon material as described in the first or third aspects of the present invention under oxidative dehydrogenation reaction conditions.
According to the hydrocarbon oxidative dehydrogenation reaction method of the present invention, the heteroatom-containing carbon material may be used directly for contacting with a hydrocarbon, or the heteroatom-containing carbon material may be molded and then used for contacting with a hydrocarbon.
The hydrocarbon oxidative dehydrogenation reaction process according to the present invention can dehydrogenate various types of hydrocarbons to obtain unsaturated hydrocarbons such as olefins. The process according to the invention is particularly suitable for dehydrogenating alkanes, thereby obtaining alkenes.
In the present invention, the hydrocarbon is preferably an alkane, such as C2-C12Of (a) an alkane. Specifically, the hydrocarbon may be, but not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2-ethylpentane, 3-ethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2, 3-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3-ethylhexane, 2, 3-trimethylpentane, 2,3, 3-trimethylpentane, 2,4, 4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2, 3-dimethylheptane, 2, 4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3, 4-trimethylhexane, 2,3, 5-trimethylhexane, 2,4, 5-trimethylhexane, 2, 3-trimethylhexane, 2, 4-trimethylhexane, 2, 5-trimethylhexane, 2,3, 3-trimethylhexane, 2,4, 4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various isomers of trimethylcyclohexane, such as 1,2, 3-trimethylcyclohexane, 1,2, 4-trimethylcyclohexane, 1,2, 5-trimethylcyclohexane, 1,3, 5-trimethylcyclohexane), n-decane, 2-methylnonane, 3-methylnonane4-methylnonane, 5-methylnonane, 2, 3-dimethyloctane, 2, 4-dimethyloctane, 3-ethyloctane, 4-ethyloctane, 2,3, 4-trimethylheptane, 2,3, 5-trimethylheptane, 2,3, 6-trimethylheptane, 2,4, 5-trimethylheptane, 2,4, 6-trimethylheptane, 2, 3-trimethylheptane, 2, 4-trimethylheptane, 2, 5-trimethylheptane, 2, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3-diethylhexane, 3, 4-diethylhexane, 2-methyl-3, 3-diethylpentane, phenylethane, 1-phenylpropane, 2-phenylpropane, 1-phenylbutane, 2-phenylbutane, 1-phenylpentane, 2-phenylpentane and 3-phenylpentane. More preferably, the hydrocarbon is one or two or more of propane, n-butane, isobutane and phenylethane. Further preferably, the hydrocarbon is n-butane.
The amount of oxygen used in the process for the oxidative dehydrogenation of hydrocarbons according to the present invention may be conventionally selected. Generally, the molar ratio of hydrocarbon to oxygen may be from 0.2 to 3: 1, preferably 0.5 to 2.5: 1, more preferably 1-2: 1.
according to the hydrocarbon oxidative dehydrogenation reaction method, the hydrocarbon and optional oxygen can be fed into the reactor by the carrier gas to contact and react with the heteroatom-containing carbon material. The carrier gas may be a commonly used gas that does not chemically interact with the reactants and the reaction product under the reaction conditions and does not undergo decomposition, such as one or a combination of two or more of nitrogen, carbon dioxide, a noble gas, and water vapor. The amount of carrier gas may be conventionally selected. Generally, the content of the carrier gas may be 30 to 99.5% by volume, preferably 50 to 99% by volume, more preferably 70 to 98% by volume.
In the process for the oxidative dehydrogenation of hydrocarbons according to the present invention, the temperature of the contacting may be conventionally selected to be sufficient to effect dehydrogenation of the hydrocarbon. Generally, the contacting may be performed at a temperature of 200-650 ℃, preferably at a temperature of 300-600 ℃, more preferably at a temperature of 350-550 ℃, and even more preferably at a temperature of 400-450 ℃.
According to the process for the oxidative dehydrogenation of hydrocarbons of the present invention, the contact may be carried out in a fixed bed reactor or a fluidized bed reactor, and is not particularly limited. Preferably, the contacting is carried out in a fixed bed reactor.
According to the hydrocarbon oxidative dehydrogenation reaction process of the present invention, the duration of the contacting can be selected according to the contacting temperature, for example, when the contacting is carried out in a fixed bed reactor, the duration of the contacting can be expressed in terms of the gas hourly volume space velocity of the feed. Generally, the gas hourly space velocity of the feed can be 500-2000h-1Preferably 800--1。
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, X-ray photoelectron spectroscopy was carried out on an ESCALB 250 type X-ray photoelectron spectrometer equipped with Thermo Avantage V5.926 software, manufactured by Thermo Scientific, with an excitation source of monochromated Al K.alpha.X rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, and a base vacuum of 6.5X 10 during analytical testing-10mbar, electron binding energy was corrected for the C1s peak (284.6eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
In the following examples and comparative examples, the ASAP2000 type N from micrometrics, USA, was used2The physical adsorption instrument measures the specific surface area, and the volume average particle size is measured on a laser particle analyzer.
In the following examples and comparative examples, elemental analysis was performed on an Elementar Micro Cube elemental analyzer, and the specific operating methods and conditions were as follows: weighing 1-2mg of sample in a tin cup, placing the sample in an automatic sample feeding disc, feeding the sample into a combustion tube through a ball valve for combustion, wherein the combustion temperature is 1000 ℃ (for removing atmospheric interference during sample feeding, helium gas is adopted for blowing), and then reducing the combusted gas by using reduced copper to form nitrogen, carbon dioxide and water. The mixed gas is separated by three desorption columns and sequentially enters a TCD detector for detection. The oxygen element is analyzed by converting oxygen in a sample into CO under the action of a carbon catalyst by utilizing pyrolysis, and then detecting the CO by adopting TCD.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer of the Japanese physical D/MAX-2500 type, using CuK α rays, at an operating voltage of 20kV, at a tube current of 10mA, and in a scanning range of 5 to 70 °.
Examples 1-9 serve to illustrate the invention.
Example 1
Activated carbon (purchased from green world activated carbon Co., Ltd., volume average particle diameter of 200 μm, property parameters of which are shown in Table 1) as a raw material carbon material having an X-ray diffraction spectrum in which dispersion peaks were present at 2 theta angles of 20 to 30 DEG and 40 to 50 DEG, respectively, and diffraction peaks and sharp peaks were not present at the remaining positions) was calcined at 500 ℃ for 5 hours in a tube furnace, during the roasting process, a reactive atmosphere consisting of ammonia gas, water vapor and nitrogen gas (wherein, the content of the ammonia gas is 3 volume percent, and the content of the water vapor is 2 volume percent) is continuously introduced into the tubular furnace, after the roasting and sintering are finished, the temperature of the tube furnace was naturally cooled to room temperature while maintaining the above reactive atmosphere, to obtain a heteroatom-containing carbon material (volume average particle diameter: 205 μm) according to the present invention, the property parameters of which are listed in Table 1.
Example 2
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the calcination temperature was 700 ℃ to thereby obtain a heteroatom-containing carbon material (volume-average particle diameter: 210 μm) according to the present invention, property parameters of which are shown in Table 1, and an X-ray diffraction spectrum of which there were dispersion peaks at 2. theta. angles of between 20 ℃ and 30 ℃ and between 40 ℃ and 50 ℃, respectively.
Example 3
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the calcination temperature was 900 ℃ to thereby obtain a heteroatom-containing carbon material (volume-average particle diameter: 209 μm) according to the present invention, property parameters of which are shown in Table 1, and an X-ray diffraction spectrum of which there were dispersion peaks at 2. theta. angles of between 20 ℃ and 30 ℃ and between 40 ℃ and 50 ℃, respectively.
Example 4
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the calcination temperature was 1000 ℃ to obtain a heteroatom-containing carbon material (volume-average particle diameter: 202 μm) according to the present invention, the property parameters of which are shown in Table 1, and which had X-ray diffraction patterns having dispersion peaks at 2. theta. angles of 20 to 30 ℃ and 40 to 50 ℃, respectively.
Example 5
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the calcination temperature was 1200 ℃ to obtain a heteroatom-containing carbon material (volume-average particle diameter: 198 μm) according to the present invention, property parameters of which are shown in Table 1, and an X-ray diffraction spectrum of which dispersion peaks were present at 2. theta. angles of 20 to 30 ℃ and 40 to 50 ℃, respectively.
Example 6
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the calcination temperature was 400 ℃ to obtain a heteroatom-containing carbon material (volume-average particle diameter of 203 μm) according to the present invention, property parameters of which are shown in Table 1, and an X-ray diffraction pattern of which dispersion peaks were present at 2. theta. angles of 20 to 30 ℃ and 40 to 50 ℃, respectively.
Example 7
A heteroatom-containing carbon material was prepared in the same manner as in example 1 except that the reactive atmosphere contained no water vapor, thereby obtaining a heteroatom-containing carbon material (volume average particle diameter: 208 μm) according to the present invention, property parameters of which are shown in Table 1, and an X-ray diffraction spectrum of which there were dispersion peaks at 2. theta. angles of between 20 ° and 30 ° and between 40 ° and 50 °, respectively.
Comparative example 1
A heteroatom-containing carbon material was prepared in the same manner as in example 2, except that carbon nanotubes (available from Oncam organic chemistry, Inc., of Chinese academy of sciences, whose property parameters are shown in Table 1) were used as the raw material carbon material, and the property parameters of the obtained heteroatom-containing carbon tube were shown in Table 1.
Comparative example 2
A heteroatom-containing carbon material was prepared in the same manner as in example 1, except that the reactive atmosphere contained no ammonia gas, and the property parameters of the resulting product were as listed in Table 1.
Comparative example 3
A heteroatom-containing carbon material was prepared in the same manner as in example 1, except that the calcination temperature was 300 ℃ and the property parameters of the resulting product were as shown in Table 1.
Comparative example 4
A heteroatom-containing nanocarbon material was prepared in the same manner as in example 1, except that the calcination temperature was 1500 ℃ and the property parameters of the obtained product were as shown in Table 1.
Example 8
Activated carbon (purchased from Beijing chemical reagent company, volume average particle size of 120 μm, property parameters of which are listed in Table 1) as a raw material carbon material was calcined at 800 ℃ for 3 hours in a tubular furnace in an X-ray diffraction spectrum of the raw material carbon material in which dispersion peaks were present between 20 DEG and 30 DEG and between 40 DEG and 50 DEG, respectively, and no diffraction peak and sharp peak were present at the remaining positions, a reactive atmosphere consisting of ammonia gas, water vapor and nitrogen gas (wherein the content of ammonia gas was 1.5% by volume and the content of water vapor was 1% by volume) was continuously introduced into the tubular furnace during the calcination, and after the calcination, the reactive atmosphere was maintained, the temperature of the tubular furnace was naturally cooled to room temperature to obtain a heteroatom-containing carbon material (volume average particle size of 123 μm) according to the present invention, the property parameters of which are listed in Table 1, in an X-ray diffraction spectrum of the carbon material containing the heteroatom, dispersion peaks exist between 20 degrees and 30 degrees and between 40 degrees and 50 degrees of a 2 theta angle respectively.
Example 9
Activated carbon (purchased from Beijing chemical reagent company, volume average particle size of 80 μm, property parameters of which are listed in Table 1) as a raw material carbon material of which X-ray diffraction spectrum has dispersion peaks between 20 DEG and 30 DEG and between 40 DEG and 50 DEG, respectively, and no diffraction peak and sharp peak at the rest positions was calcined at 800 ℃ for 2 hours, a reactive atmosphere consisting of ammonia gas, water vapor and nitrogen gas (wherein the content of ammonia gas is 0.5 vol%, and the content of water vapor is 0.5 vol%) was continuously introduced into the tubular furnace during the calcination, after the calcination, the reactive atmosphere was maintained, the temperature of the tubular furnace was naturally cooled to room temperature to obtain a heteroatom-containing carbon material (volume average particle size of 87 μm) according to the present invention, property parameters of which are listed in Table 1, in an X-ray diffraction spectrum of the carbon material containing the heteroatom, dispersion peaks exist between 20 degrees and 30 degrees and between 40 degrees and 50 degrees of a 2 theta angle respectively.
TABLE 1
1: raw material carbon material used in example 1
2: carbon nanotubes used as raw materials in comparative example 1
3: example 8 carbon Material
4: raw material carbon Material for example 9
5: the oxygen content determined by X-ray photoelectron spectroscopy was a, and the oxygen content determined by elemental analysis was b.
Fig. 1 shows an X-ray diffraction pattern of the raw material carbon material used in example 1, and fig. 2 shows an X-ray diffraction pattern of the heteroatom-containing carbon material prepared in example 1. As can be seen from FIG. 2, the heteroatom-containing carbon material prepared in example 1 had dispersion peaks at 2 θ angles of 20 ° to 30 ° and 40 ° to 50 °, respectively. Fig. 3 and 4 show X-ray diffraction patterns of the carbon nanotube used as a raw material in comparative example 1 and the heteroatom-containing carbon nanotube prepared in comparative example 1, respectively, and it can be seen from fig. 4 that the heteroatom-containing nanocarbon material prepared in comparative example 1 still maintains the regular structure of the carbon nanotube.
Experimental examples 1 to 9
The heteroatom-containing carbon materials prepared in examples 1 to 9 were used as catalysts for oxidative dehydrogenation of n-butane, respectively, and n-butane oxidative dehydrogenation reaction was carried out as follows.
0.2g (packing volume of 0.5mL) of the heteroatom-containing carbon material prepared in examples 1 to 9 as a catalyst was packed in a universal fixed bed miniature quartz tube reactor each having quartz sand sealed at both ends, and under normal pressure (i.e., 1 atm) and 400 ℃ conditions, a gas containing n-butane and oxygen (n-butane concentration of 1.0 vol%, n-butane and oxygen molar ratio of 1: 2, and balance nitrogen as a carrier gas) was fed at a total volume space velocity of 1200h-1The reaction was conducted by passing it into the reactor, and the composition of the reaction mixture discharged from the reactor was continuously monitored, and the n-butane conversion, the total olefin selectivity, and the n-butene selectivity were calculated, and the results of the reaction for 5 hours are shown in Table 2.
Experimental comparative examples 1 to 4
The oxidative dehydrogenation of butane was carried out in the same manner as in experimental examples 1 to 9, except that the catalyst used was the product prepared in comparative examples 1 to 4, and the results of the reaction for 5 hours were as shown in Table 2.
Comparative Experimental examples 1 to 4
The oxidative dehydrogenation of butane was carried out in the same manner as in experimental examples 1 to 9, except that the raw material carbon materials of examples 1, 8 and 9 and the raw material carbon nanotubes of comparative example 1 were used as catalysts, and the results of the reaction for 5 hours were shown in Table 2.
TABLE 2
1: the raw material carbon material used in example 1 was usedAs catalysts2: the carbon nanotubes used in comparative example 1 as the starting material were used as the catalyst
3: the raw material carbon material used in example 8 was used as a catalyst4: the raw material carbon material used in example 9 was used as a catalyst
The results in Table 2 demonstrate that the use of the heteroatom-containing carbon material of the present invention as a catalyst for the oxidative dehydrogenation of hydrocarbons greatly improves the selectivity to olefins. Although the existing catalyst can obtain higher n-butane conversion rate, the olefin selectivity is lower, so most n-butane is combusted inefficiently, and the heteroatom-containing carbon material is used as the catalyst for the oxidative dehydrogenation reaction of hydrocarbon, the unconverted n-butane can be separated and recycled although the n-butane conversion rate is reduced, so that the overall utilization rate of raw materials is improved. In addition, the carbon material containing the heteroatom adopts the amorphous carbon with low price as the raw material, the preparation process is simple, and the manufacturing cost is obviously reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (42)
1. A heteroatom-containing carbon material containing an oxygen element in an amount of 1 to 10% by weight, a nitrogen element in an amount of 0.01 to 4% by weight, a hydrogen element in an amount of 0.1 to 3% by weight, and a carbon element in an amount of 83 to 98.89% by weight, based on the total amount of the heteroatom-containing carbon material and calculated as the elements,
in an X-ray diffraction pattern of the carbon material containing the heteroatom, dispersion peaks exist respectively at the 2 theta angle of 20-30 degrees and at the 2 theta angle of 40-50 degrees;
in the heteroatom-containing carbon material, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by an elemental analysis method is b, and a/b is more than or equal to 2.
2. The heteroatom-containing carbon material of claim 1, wherein a/b is 2 to 5.
3. The heteroatom-containing carbon material as claimed in claim 2, wherein a/b is 2.1 to 4.5.
4. The heteroatom-containing carbon material as claimed in any one of claims 1 to 3, wherein the content of oxygen element is 1.2 to 8% by weight, the content of nitrogen element is 0.03 to 3% by weight, the content of hydrogen element is 0.2 to 2.5% by weight, and the content of carbon element is 86.5 to 98.57% by weight, based on the total amount of the heteroatom-containing carbon material and calculated as elements.
5. The heteroatom-containing carbon material as claimed in claim 4, wherein the content of the oxygen element is 1.5 to 6% by weight, the content of the nitrogen element is 0.05 to 2% by weight, the content of the hydrogen element is 0.4 to 2% by weight, and the content of the carbon element is 90 to 98.05% by weight, based on the total amount of the heteroatom-containing carbon material and calculated as elements.
6. The heteroatom-containing carbon material as claimed in any one of claims 1 to 3, wherein the specific surface area of the heteroatom-containing carbon material is 100m or more2/g。
7. The heteroatom-containing carbon material as claimed in claim 6, wherein the specific surface area of the heteroatom-containing carbon material is 500m or more2/g。
8. The heteroatom-containing carbon material as claimed in claim 7, wherein the specific surface area of the heteroatom-containing carbon material is 600m or more2/g。
9. The heteroatom-containing carbon material as claimed in claim 8, wherein the heteroatom is containedThe specific surface area of the daughter carbon material is 700-1500m2/g。
10. A method for producing a heteroatom-containing carbon material, the method comprising: roasting a raw material carbon material at the temperature of 400-1200 ℃ in a reactive atmosphere, wherein the reactive atmosphere contains ammonia gas, optional carrier gas and optional water vapor;
the raw material carbon material contains oxygen element, hydrogen element and carbon element, wherein the content of the oxygen element is 0.2-12 wt%, the content of the hydrogen element is 0.05-3 wt%, and the content of the carbon element is 85-99.75 wt% based on the total amount of the raw material carbon material and calculated by the elements;
in an X-ray diffraction pattern of the raw material carbon material, dispersion peaks exist between 20 degrees and 30 degrees of a 2 theta angle and between 40 degrees and 50 degrees respectively;
in the raw material carbon material, the content of surface oxygen determined by X-ray photoelectron spectroscopy is a, the content of bulk oxygen determined by an elemental analysis method is b, and a/b is less than 2.
11. The method of claim 10, wherein the reactive atmosphere contains water vapor, and the water vapor is present in the reactive atmosphere in an amount of 0.01 to 10 vol%.
12. The method of claim 11, wherein the reactive atmosphere contains water vapor, and the water vapor is present in the reactive atmosphere in an amount of 0.1 to 9 vol%.
13. The method of claim 12, wherein the reactive atmosphere contains water vapor, and the water vapor is present in the reactive atmosphere in an amount of 0.2 to 5 vol%.
14. The method of claim 13, wherein the reactive atmosphere contains water vapor, and the water vapor is present in the reactive atmosphere in an amount of 0.5 to 2 vol%.
15. The method according to any one of claims 10 to 14, wherein the reactive atmosphere comprises ammonia in an amount of 0.01 to 5% by volume.
16. The method of claim 15, wherein the reactive atmosphere has an ammonia gas content of 0.1-4 vol%.
17. The method of claim 16, wherein the reactive atmosphere has an ammonia gas content of 0.5-3 vol%.
18. The method of claim 10, wherein a/b is 0.9-1.95.
19. The method of claim 18, wherein a/b is 1.2-1.9.
20. The method according to any one of claims 10, 18, and 19, wherein the content of the oxygen element is 0.5 to 10% by weight, the content of the hydrogen element is 0.1 to 3% by weight, and the content of the carbon element is 87 to 99.4% by weight, based on the total amount of the raw material carbon material and calculated as an element.
21. The method according to claim 20, wherein the content of the oxygen element is 1 to 9.5% by weight, the content of the hydrogen element is 0.5 to 2.8% by weight, and the content of the carbon element is 87.7 to 98.5% by weight, in terms of element, based on the total amount of the raw material carbon material.
22. The method according to claim 21, wherein the content of the oxygen element is 2 to 9% by weight in terms of element based on the total amount of the raw material carbon material; the content of the hydrogen element is 1-2.6 wt%; the content of the carbon element is 88.4-97 wt%.
23. The method of any one of claims 10, 18 and 19, wherein the feedstock is a feedstock for a chemical plantThe specific surface area of the carbon material is 400-1400m2/g。
24. The method as claimed in claim 23, wherein the specific surface area of the raw material carbon material is 600-1300m2/g。
25. The method as claimed in claim 24, wherein the specific surface area of the raw material carbon material is 800-1200m2/g。
26. The method of any one of claims 10, 18, and 19, wherein the feedstock carbon material is activated carbon.
27. The method as claimed in claim 10, wherein the calcination is carried out at a temperature of 500-1100 ℃.
28. The method as claimed in claim 27, wherein the calcination is carried out at a temperature of 700-.
29. The method of any one of claims 10, 27 and 28, wherein the duration of the firing is 0.5-24 hours.
30. The method of claim 29, wherein the duration of the firing is 1-8 hours.
31. The method of claim 30, wherein the duration of the firing is 2-6 hours.
32. A heteroatom-containing carbon material produced by the method of any one of claims 10-31.
33. Use of the heteroatom-containing carbon material of any one of claims 1 to 9 and 32 as a catalyst for oxidative dehydrogenation of hydrocarbons.
34. Use according to claim 33, wherein the hydrocarbon is an alkane.
35. Use according to claim 34, wherein the hydrocarbon is C2-C12Of (a) an alkane.
36. Use according to claim 35, wherein the hydrocarbon is butane.
37. Use according to claim 36, wherein the hydrocarbon is n-butane.
38. A process for the oxidative dehydrogenation of a hydrocarbon, the process comprising contacting the hydrocarbon with the heteroatom-containing carbon material of any one of claims 1-9 and 32 under oxidative dehydrogenation reaction conditions.
39. The method of claim 38, wherein the hydrocarbon is an alkane.
40. The method of claim 39, wherein the hydrocarbon is C2-C12Of (a) an alkane.
41. The method of claim 40, wherein the hydrocarbon is butane.
42. The method of claim 41, wherein the hydrocarbon is n-butane.
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