CN107445787B - Application of graphitized activated carbon material as catalyst for oxidative dehydrogenation reaction of n-butane - Google Patents

Application of graphitized activated carbon material as catalyst for oxidative dehydrogenation reaction of n-butane Download PDF

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CN107445787B
CN107445787B CN201710724426.5A CN201710724426A CN107445787B CN 107445787 B CN107445787 B CN 107445787B CN 201710724426 A CN201710724426 A CN 201710724426A CN 107445787 B CN107445787 B CN 107445787B
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butane
activated carbon
catalyst
oxidative dehydrogenation
carbon material
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CN107445787A (en
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刘洪阳
张雅洁
苏党生
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Institute of Metal Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon

Abstract

The invention discloses an application of a graphitized activated carbon material as a catalyst for an n-butane oxidative dehydrogenation reaction, and belongs to the technical field of catalysts for the n-butane oxidative dehydrogenation reaction. The graphitized activated carbon material is obtained by heating and roasting activated carbon in an inert atmosphere. The catalyst catalyzes n-butane to perform oxidative dehydrogenation to generate butadiene under the condition of no water vapor protection, and the use temperature of the catalyst is 350-450 ℃; the catalytic reaction conditions are as follows: the air speed is 1000-18000 ml/g.h, the volume concentration of n-butane is 1-5%, and the volume ratio of n-butane to oxygen is 1: 0.5-1: 5; compared with the traditional unmodified carbon catalyst, the graphitized activated carbon catalyst can effectively catalyze butane to be converted into olefin, and the dehydrogenation selectivity and the yield are obviously improved. The catalyst has good stability and oxidation resistance, is not easy to burn and inactivate in the reaction process, is not easy to deposit carbon, and does not need steam protection.

Description

Application of graphitized activated carbon material as catalyst for oxidative dehydrogenation reaction of n-butane
Technical Field
The invention relates to the technical field of n-butane oxidative dehydrogenation reaction catalysts, in particular to application of a graphitized activated carbon material as an n-butane oxidative dehydrogenation reaction catalyst.
Background
Low carbon alkane (C)1-C4) Dehydrogenation is an important catalytic reaction process in chemical production. The alkane has low price and wide source, and the corresponding olefin products such as ethylene and butylene are chemical intermediates which are greatly required in the downstream chemical industry, so the alkane has high economic added value. One of the main uses of n-butane at present is dehydrogenation to produce butylene and butadiene, and further synthesize rubber and resin and other chemical products with large market demand, so that the reaction of n-butane dehydrogenation has great economic benefit. With the continuous development of future oil refining industry in China, the capacity of newly added liquefied petroleum gas is increased year by year, and ten million tons of liquefied petroleum gas are predicted to be newly added in China during the thirteen-five period. However, due to the influence of cheap natural gas, the price of the liquefied petroleum gas and other petroleum products are at presentCompared with the prior art, the product is at the low end, the olefin with high added value is prepared by developing a new environment-friendly and high-efficiency nonmetal catalyst to catalyze the dehydrogenation of the low-carbon alkane, the added value of the original low-carbon alkane in the liquefied petroleum gas is improved, and the method has great economic benefit and is also an important opportunity for the sustainable development of the petrochemical industry.
The traditional activated carbon has high specific surface area, developed pores and good acid and alkali resistance, and is often widely applied to the catalytic industry as an adsorbent and a catalyst carrier. The 20 th century, 60 s, have discovered that the active center of the ethylbenzene oxidative dehydrogenation reaction may be derived from carbon deposited on the surface of the iron oxide catalyst, and since that time, it was recognized that the carbon material itself may also be a catalyst for the oxidative dehydrogenation reaction. Meanwhile, the surface of the activated carbon has rich chemical groups, and the graphite carbon and the amorphous carbon coexist to ensure that the surface physical and chemical properties of the graphite carbon and the amorphous carbon are adjustable, so that an active center with catalytic performance is generated, and therefore, in many reactions, the activated carbon can be used as an ideal nonmetal catalyst to catalyze reactions, and particularly shows better catalytic performance in oxidation-reduction reactions, such as ethylbenzene oxidative dehydrogenation, ethylbenzene direct dehydrogenation-nitrobenzene reduction coupling, flue gas desulfurization and the like. And the activated carbon is easy to recover and degrade, is environment-friendly, has mature manufacturing process, low cost and wide sources, and is a nonmetal catalyst with great industrial application prospect. However, the practical application of the activated carbon catalyst in the gas phase oxidative dehydrogenation reaction is limited by the defects that the traditional activated carbon material has high disorder degree and poor oxidation resistance, is easy to burn in the oxidative dehydrogenation reaction, has high micropore quantity and is easy to be blocked by carbon deposition and further inactivated.
Disclosure of Invention
The invention aims to provide an application of a graphitized activated carbon material as a catalyst for n-butane oxidative dehydrogenation reaction, wherein the graphitized activated carbon material is a non-metal catalyst capable of catalyzing n-butane oxidative dehydrogenation reaction, the catalyst has better oxidation resistance, and can catalyze n-butane oxidative dehydrogenation to generate C with high selectivity in an oxygen atmosphere at 350-450 DEG C4Olefin and maintains better stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the graphitized activated carbon material is used as a catalyst for the oxidative dehydrogenation reaction of n-butane to generate C by catalyzing the oxidative dehydrogenation of the n-butane under the condition of no water vapor protection4An olefin.
The graphitized activated carbon material is obtained by taking activated carbon as a raw material and roasting at a high temperature for modification; the activated carbon comprises an activated carbon material industrially produced by a traditional process and activated carbon prepared by novel biomass conversion. The specific process of high-temperature roasting modification comprises the following steps: 1-2g of activated carbon is put into an alumina crucible, then the crucible is placed into a tubular furnace, inert argon is introduced at the flow rate of 50-100mL/min, the furnace body is programmed to be heated to 800-1600 ℃ after being purged for 30min, the temperature is kept for 1-4h, and then the temperature is reduced to room temperature, thus obtaining the graphitized activated carbon material.
The specific surface area of the graphitized activated carbon material is 800-1000m2/g, sp of the modified carbon material compared with the unmodified carbon material2The hybridization degree is increased, the graphitization degree is obviously increased, and the material has graphitized crystal lattices. The carbon material with the increased graphitization degree has more graphite layer edges, and the graphite layer edges are easy to generate more dehydrogenation active center C ═ O functional groups in the butane oxidative dehydrogenation reaction process, so that the selectivity of the product olefin is obviously improved.
In the process of the n-butane oxidation dehydrogenation reaction, the using temperature of the catalyst is 350-450 ℃; the catalytic reaction conditions are as follows: the air speed is 1000-18000 ml/g.h, the volume concentration of n-butane is 1-5%, and the volume ratio of n-butane to oxygen is 1: 0.5-1: 5.
The design principle of the invention is as follows:
in order to confirm the active center on the activated carbon catalyst and improve the oxidation resistance, the oxygen functional group on the surface of the activated carbon and the carbon hybrid structure thereof are researched; the results show that the carbonyl oxygen functional groups on the surface of the activated carbon are active centers for catalyzing oxidative dehydrogenation reactions. These oxygen functional groups are also generated at the edge of the graphite carbon layer. Therefore, how to simply, conveniently and efficiently control the partial graphitization of the activated carbon material, and maintain the high specific surface area while simultaneously controlling the partial graphitization of the activated carbon materialImproving the oxidation resistance of the activated carbon catalyst is the key to realizing the application of the activated carbon catalyst in the catalytic reaction of low-carbon alkane. The invention carries out high graphitization on the activated carbon material by a specific high-temperature roasting process to obtain the graphitized activated carbon material with the specific surface area of 800-1000m2/g, sp of the modified carbon material compared with the unmodified carbon material2The hybridization degree is increased, the graphitization degree is obviously increased, and obvious graphitization crystal lattices can be seen in an electron microscope picture.
The novel graphitized activated carbon material has more graphite layer edges, and the graphite layer edges easily generate more dehydrogenation active centers C ═ O functional groups in the butane oxidative dehydrogenation reaction process, so that the product C is obviously improved4Selectivity to olefins (butenes and butadiene). Meanwhile, the novel graphitized activated carbon material has good oxidation resistance and shows high stability and carbon deposit resistance in oxidative dehydrogenation reaction.
The invention has the following advantages:
1. the invention adopts the novel graphitized activated carbon material as the catalyst for the oxidative dehydrogenation reaction of the n-butane, the catalyst has higher graphitization degree, shows better dehydrogenation selectivity in the oxidative dehydrogenation reaction process of the butane, and improves the yield of the product olefin. Wherein the conversion rate of n-butane is 12-30%, C4The olefin selectivity is 40-60%.
2. The invention adopts the novel graphitized activated carbon material as the catalyst for the oxidative dehydrogenation reaction of the n-butane, the catalyst has good oxidation resistance, shows higher stability and carbon deposit resistance in the oxidative dehydrogenation reaction, and has the service life of more than or equal to 50 hours at the reaction temperature of 400 ℃.
3. The catalyst used in the invention has mature production process, simple and convenient modification method, low cost and large-scale production, does not contain metal, has no pollution to the environment, and is environment-friendly and efficient.
Drawings
FIG. 1 shows TEM characterization results of carbon materials; wherein: (A) comparative example 1; (B) example 1; (C) example 2; (D) example 3; .
FIG. 2 shows the characterization results of the carbon material TPO.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
1g of activated carbon material is put into an alumina crucible, the alumina crucible is placed into a high-temperature tubular furnace, inert argon is introduced at the flow rate of 100mL/min, the furnace body is programmed to be heated to 900 ℃, the temperature is kept for 1h and then is programmed to be cooled to the room temperature, and the catalyst is taken out and recorded as 900 AC.
Weighing 100mg of calcined catalyst 900AC, filling into a phi 10 fixed bed quartz tube, introducing a mixed feed gas of 2% n-butane and 4% oxygen at the flow rate of 15mL/min, reacting at 450 ℃ for 12h, continuously detecting the gas after the reaction by gas chromatography, and not finding the catalyst deactivation phenomenon in the reaction process. N-butane conversion 39%, C4The olefin selectivity was 28% and the yield was 10.4%.
Example 2
The calcination temperature was raised to 1300 ℃ in example 1, and the modified catalyst was designated 1300 AC. Weighing 100mg of catalyst 1300AC, filling the catalyst into a phi 10 fixed bed quartz tube, introducing mixed feed gas of 2% n-butane and 4% oxygen at the flow rate of 15mL/min, reacting for 12h at 450 ℃, continuously detecting the gas after the reaction by gas chromatography, and not finding the catalyst deactivation phenomenon in the reaction process. N-butane conversion 35%, C4The olefin selectivity was 33% and the yield was 11.8%.
Example 3
The calcination temperature was raised to 1500 ℃ in example 1 and the modified catalyst was designated 1500 AC. Weighing 100mg of catalyst 1500AC, filling into a phi 10 fixed bed quartz tube, introducing a mixed feed gas of 2% n-butane and 4% oxygen at the flow rate of 15mL/min, reacting at 450 ℃ for 12h, continuously detecting the gas after the reaction by gas chromatography, and not finding the catalyst deactivation phenomenon in the reaction process. N-butane conversion 32%, C4The olefin selectivity was 42% and the yield was 13.2%.
Example 4
The 1500AC catalyst obtained in example 3 was loaded into a phi 10 fixed bed quartz tube, a mixed raw material gas of 2% n-butane and 4% oxygen was introduced at a flow rate of 15mL/min, and reacted at 400 ℃ for 50 hours, after which the gas was subjected to gas chromatographyContinuous detection, the conversion rate of the n-butane is 12 percent, C4The selectivity of olefin is 61%, the yield is 7.3%, and the catalyst deactivation phenomenon is not found in the reaction process, which shows that the modification method of the invention can obviously improve the oxidative dehydrogenation stability of the traditional carbon catalyst.
Comparative examples 1 to 2
Comparative examples 1 and 2 are unmodified activated carbon AC and carbon nanotube CNTs calcined at a high temperature of 900 ℃, respectively. 100mg of the catalyst used as butane oxidative dehydrogenation catalyst was also weighed out separately and reacted at 450 ℃ for 12 hours, and the gas was continuously detected by gas chromatography after the reaction. The active carbon AC catalyst has obvious inactivation and loss of catalyst quality. C4The olefin selectivity and its yield are summarized in table 1:
TABLE 1 comparison of catalytic Activity after 12 hours of oxidative dehydrogenation of butane
Catalyst and process for preparing same C4Olefin selectivity C4Olefin yield
Comparative example 1AC 23％ 8.5％
Example 1900 AC 28％ 10.4％
Example 21300 AC 33％ 11.8％
Example 31500 AC 42％ 13.2％
Comparative example 2CNTs 34％ 5.1％
The result proves that the novel graphitized activated carbon catalyst can effectively catalyze butane oxidative dehydrogenation reaction to obtain C with high selectivity and high yield4An olefin.
By observing the degree of order of the crystal grains in examples 1 to 3 and comparative example 1 with a high-resolution electron microscope (TEM) (fig. 1), it can be found that the surface of the novel graphitized activated carbon material is partially graphitized, the graphitization degree of the novel graphitized activated carbon material is increased along with the rise of the roasting temperature, the crystal lattice stripes are ordered, and the lattice spacing is close to that of the graphite crystal. The surface graphitization degree and the hybridization degree of the novel graphitized activated carbon material can be regulated and controlled.
Comparative examples 1-2 and examples 1-3 were evaluated using a Temperature-programmed oxidation (TPO) characterization procedure, which recorded the change in sample mass with Temperature using a thermogravimetric analyzer measurement, and specifically included:
weighing 5mg of sample, placing the sample into an alumina crucible and placing the alumina crucible on a tray of a thermogravimetric analyzer, introducing 10% oxygen-argon mixed gas at the flow rate of 50mL/min, raising the temperature from room temperature to 1000 ℃ by a program of 10 ℃/min, measuring and recording the weight change of the sample by a thermogravimetric balance, and obtaining the result shown in figure 2.
As can be seen from FIG. 2, the initial oxidative weight loss temperature of the graphitized activated carbon material 1500AC obtained in example 3 is higher, which is close to the highly ordered carbon nanotubes CNTs of comparative example 2 and is about 100 ℃ higher than that of the activated carbon AC of comparative example 1, thus indicating that the modified carbon catalyst of the present invention has better oxidation resistance.
The combination of the experimental results shows that the novel graphitized activated carbon material provided by the invention has high surface graphitization degree and large specific surface area, andcompared with the traditional carbon catalyst, the catalyst has good oxidation resistance, and C is used for catalyzing the oxidative dehydrogenation reaction of butane4The selectivity and yield of olefin are obviously improved, the stability of the catalyst can reach more than 50 hours under the condition of no water vapor protection, and the production problems of serious carbon deposition, high water content of butadiene product, large sewage discharge and the like of the existing butadiene dehydrogenation device can be improved. And the catalyst has mature synthesis method, convenient and easy implementation of modification process, easy recovery and environmental protection.
The above is a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment, and variations and advantages which can be conceived by those skilled in the art are also included in the present invention without departing from the spirit and scope of the inventive concept.

Claims (4)

1. The application of the graphitized activated carbon material as a catalyst for the oxidative dehydrogenation reaction of n-butane is characterized in that: the graphitized activated carbon material is used as a catalyst for the oxidative dehydrogenation reaction of n-butane to generate C by catalyzing the oxidative dehydrogenation of n-butane under the condition of no water vapor protection4An olefin;
in the process of the n-butane oxidation dehydrogenation reaction, the using temperature of the catalyst is 350-450 ℃; the catalytic reaction conditions are as follows: the air speed is 1000-18000 ml/g.h, the volume concentration of n-butane is 1-5%, and the volume ratio of n-butane to oxygen is 1: 0.5-1: 5;
the graphitized activated carbon material is obtained by taking activated carbon as a raw material and roasting at a high temperature for modification; the specific process of high-temperature roasting modification comprises the following steps: 1-2g of activated carbon is put into an alumina crucible, then the crucible is placed into a tubular furnace, inert argon is introduced at the flow rate of 50-100mL/min, the furnace body is heated to 800-.
2. The use of the graphitized activated carbon material of claim 1 as a catalyst for an n-butane oxidative dehydrogenation reaction, wherein: the activated carbon comprises an activated carbon material industrially produced by a traditional process and activated carbon prepared by novel biomass conversion.
3. The use of the graphitized activated carbon material of claim 1 as a catalyst for an n-butane oxidative dehydrogenation reaction, wherein: the specific surface area of the graphitized activated carbon material is 800-1000m2The material has graphitized crystal lattices and graphite layer edges, and the graphite layer edges generate more dehydrogenation active center C ═ O functional groups in the butane oxidative dehydrogenation reaction process, so that the product C is improved4Selectivity to olefin.
4. The use of the graphitized activated carbon material of claim 1 as a catalyst for an n-butane oxidative dehydrogenation reaction, wherein: in the process of butane oxidative dehydrogenation reaction, the conversion rate of n-butane is 12% -30%, C4The olefin selectivity is 40-60%; the service life of the catalyst is more than or equal to 50 hours at the reaction temperature of 400 ℃.
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CN105817246A (en) * 2015-01-27 2016-08-03 中国石油化工股份有限公司 Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons
CN105820023A (en) * 2015-01-27 2016-08-03 中国石油化工股份有限公司 Oxidation method for hydrocarbons
CN106362719A (en) * 2016-08-11 2017-02-01 福州大学 Modified active carbon, and preparation method and application thereof
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Publication number Priority date Publication date Assignee Title
US5510558A (en) * 1993-12-29 1996-04-23 Sun Company, Inc. (R&M) Oxidative dehydrogenation of hydrocarbons with active carbon catalyst
CN105817246A (en) * 2015-01-27 2016-08-03 中国石油化工股份有限公司 Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons
CN105820023A (en) * 2015-01-27 2016-08-03 中国石油化工股份有限公司 Oxidation method for hydrocarbons
CN107008243A (en) * 2016-01-27 2017-08-04 中国石油化工股份有限公司 A kind of nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method
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