CN112007674B - Nickel-aluminum composite material and preparation method and application thereof - Google Patents
Nickel-aluminum composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nickel-aluminum composite material and a preparation method and application thereof. The preparation method of the nickel-aluminum composite material comprises the following steps: firstly, providing a nickel-aluminum precursor; then, carrying out heating treatment on the nickel-aluminum precursor, and then carrying out hydrogen reduction treatment; cooling the nickel-aluminum precursor subjected to hydrogen reduction treatment; introducing a carbon source to carry out low-temperature vapor deposition on the nickel-aluminum precursor subjected to cooling treatment to obtain a nickel-aluminum composite material; wherein the temperature of the low-temperature vapor deposition is 200-300 ℃, and the deposition time is 30-1440 minutes. The nickel-aluminum composite material prepared by the method can completely oxidize butane in industrial waste gas at a lower temperature, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a nickel-aluminum composite material and a preparation method and application thereof.
Background
Transition metal carbides are intermetallic filled compounds formed by interstitial incorporation of carbon atoms into the crystal lattice of the transition metal. In recent years, the compound has been widely used in the fields of optics, electronics, magnetism, etc. due to its unique physical, chemical and structural properties. Especially, the high catalytic activity and selectivity of the transition metal carbide material have attracted people's attention, and the transition metal carbide material will become a new catalyst to be widely applied to the fields of petrochemical industry, automobile exhaust treatment and the like.
Since the research personnel in the sixties of the last century discovered that tungsten carbide has the electronic structure and catalytic properties similar to those of noble metals (Science, 1973,181 (4099): 547-549), the catalytic properties of transition carbides have attracted interest. Researches find that the transition metal carbide has catalytic action in many fields such as catalytic hydrogenation, catalytic dehydrogenation, catalytic hydrodesulfurization, catalytic hydrodenitrogenation, isomerization, ammonia decomposition, aromatization and the like, and has the characteristics of high catalytic activity, low price, stable performance, poisoning resistance and the like.
The metal carbides that are currently widely studied mainly include vanadium carbide, molybdenum carbide, tungsten carbide, iron carbide, titanium carbide, and the like. In contrast, nickel carbide is a less studied transition metal carbide in the field of catalysis. The preparation method of nickel carbide is mainly hydrothermal or solvothermal synthesis at present, for example, yuji Goto et al obtain nickel carbide nanoparticles by dissolving nickel acetylacetonate in oleylamine and heating to 200-320 ℃ for reaction for 1-3 hours (Chemistry of Materials,2008,20 (12): 4156-4160.).
In addition, volatile Organic Compounds (VOCs) generally refer to organic compounds having a saturated vapor pressure of greater than about 70Pa at room temperature and a boiling point of 50 to 260 ℃ or lower at normal pressure, or any organic solid or liquid that can be volatilized at room temperature and normal pressure, such as alkanes, aromatics, ether alcohols, halogenated hydrocarbons, and the like. The main sources of the volatile organic compounds are chemical or petrochemical production, building materials, interior decoration materials, living and office supplies and the like. The volatile organic compounds are important precursors for forming secondary pollutants such as fine particles, ozone and the like, and further cause atmospheric environmental problems such as dust haze, photochemical smog and the like. In addition, the medicament also has high toxicity, carcinogenic hazard and the like, has attracted wide attention at present, and becomes an important and meaningful research subject for the treatment of the medicament.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention mainly aims to provide a novel nickel-aluminum composite material and a preparation method thereof, the composite material is novel in composition and structure, contains nickel carbide and simple substance nickel, further synergistically increases the catalytic performance, is simple in preparation method, and is suitable for large-scale industrial production. In addition, the nickel-aluminum composite material can be used for completely catalyzing and oxidizing butane in industrial waste gas at a lower temperature, and has a good industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
one aspect of the present invention is to provide a nickel-aluminum composite material, wherein the nickel-aluminum composite material contains aluminum oxide, nickel carbide and elemental nickel.
According to one embodiment of the present invention, the XPS spectrum of the nickel-aluminum composite material comprises 3 Ni2p 3/2 The corresponding binding energies of the peaks are 854.0 eV-854.2 eV, 856.3 eV-856.5 eV, 859.1 eV-859.3 eV.
According to one embodiment of the present invention, the nickel-aluminum composite material has a surface nickel element content of 0.5mol% to 4mol%, a surface aluminum element content of 30mol% to 55mol%, a surface carbon element content of 13mol% to 30mol%, and a surface oxygen element content of 30mol% to 42mol%, based on the total mole amount of the surface elements of the nickel-aluminum composite material determined by XPS spectroscopy. Preferably, the nickel-aluminum composite material has a surface nickel element content of 0.5mol% to 2.5mol%, a surface aluminum element content of 40mol% to 55mol%, a surface carbon element content of 17mol% to 25mol%, and a surface oxygen element content of 30mol% to 40mol%.
According to one embodiment of the present invention, the particle size of the nickel phase in the nickel aluminum composite material is 10nm to 80nm.
In another aspect, the present invention provides a method for preparing the above nickel aluminum composite material, comprising the steps of: s1: providing a nickel-aluminum precursor; s2: carrying out heating treatment on the nickel-aluminum precursor, and then carrying out hydrogen reduction treatment; s3: cooling the nickel-aluminum precursor subjected to hydrogen reduction treatment; s4: introducing a carbon source to carry out low-temperature vapor deposition on the nickel-aluminum precursor subjected to cooling treatment to obtain a nickel-aluminum composite material; wherein the temperature of the low-temperature vapor deposition is 200-300 ℃, and the deposition time is 30-1440 minutes.
According to one embodiment of the invention, step S2 and/or step S3 is carried out with the first protective gas being passed.
According to one embodiment of the present invention, the carbon source is an alcohol, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, more preferably ethanol.
According to one embodiment of the present invention, the step of introducing a carbon source comprises:
introducing a second protective gas into the alcohol substance, and contacting the alcohol substance with the nickel-aluminum precursor subjected to cooling treatment by a bubbling carrier gas method; wherein the temperature of the alcohol substance is kept between 30 and 90 ℃.
According to one embodiment of the present invention, the first protective gas is nitrogen and/or argon, the second protective gas is nitrogen and/or argon, the flow rate of the first protective gas is 10 to 500 ml/(min. G nickel-aluminum precursor), and the flow rate of the second protective gas is 10 to 500 ml/(min. G nickel-aluminum precursor).
According to one embodiment of the present invention, the temperature increase rate in the temperature increase heat treatment is 1 ℃/min to 5 ℃/min, and the temperature decrease rate in the temperature decrease treatment is 5 ℃/min to 20 ℃/min.
According to one embodiment of the invention, the hydrogen reduction treatment comprises the step of contacting the nickel-aluminum precursor subjected to the temperature-raising heat treatment with hydrogen, wherein the temperature of the hydrogen reduction treatment is 500-900 ℃; the time is 60 minutes to 180 minutes, preferably 61 minutes to 90 minutes; the hydrogen flow is 51-200 ml/(min. G nickel-aluminum precursor).
According to one embodiment of the present invention, the structure of the nickel aluminum precursor is a hydrotalcite crystal structure.
The invention also provides the application of the nickel-aluminum composite material in catalytic oxidation of industrial waste gas, which comprises the following steps: the nickel-aluminum composite material is used as a catalyst to contact with industrial waste gas for catalytic oxidation reaction, wherein the industrial waste gas is the waste gas generated in the production process for preparing maleic anhydride by industrial n-butane oxidation.
According to one embodiment of the invention, the catalytic oxidation reaction is carried out at a temperature of 200-500 ℃, and the reaction space velocity is 2000-5000 ml industrial waste gas/(h.g nickel-aluminum composite material); the butane accounts for 0.01 to 2 volume percent of the content of the industrial waste gas in percentage by volume.
The invention has the beneficial effects that:
the invention provides a novel nickel-aluminum composite material and a preparation method and application thereof. The nickel-aluminum composite material containing nickel carbide is obtained by a method of firstly carrying out high-temperature hydrogen reduction and then carrying out low-temperature carbon deposition, the composite material is novel and unique in composition and structure, and simultaneously contains nickel carbide and elemental nickel, so that the catalytic performance is further improved in a synergistic manner; the preparation method is simple and suitable for large-scale industrial production; in addition, the composite material can also completely oxidize the low-concentration butane in the waste gas generated in the production process for preparing the maleic anhydride by oxidizing the industrial n-butane at a lower temperature, and has good industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction pattern (XRD) of the nickel aluminum composite material prepared in example 1;
FIGS. 2 and 3 are high-power transmission electron micrographs (HRTEM) of the nickel-aluminum composite material prepared in example 1 at different magnifications, respectively;
FIG. 4 is an XPS spectrum of the surface nickel of the nickel-aluminum composite material prepared in example 1;
fig. 5 is XRD spectra of the nickel aluminum composite materials prepared in comparative example 1 and comparative example 2;
FIG. 6 is a high power transmission electron micrograph (HRTEM) of the nickel aluminum composite prepared in comparative example 1;
FIG. 7 is a high power transmission electron micrograph (HRTEM) of the nickel aluminum composite prepared in comparative example 2.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to be limiting. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these 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 yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a nickel-aluminum composite material, which contains aluminum oxide, nickel carbide and simple substance nickel.
According to the invention, the nickel-aluminum composite material is a material with good catalytic activity, however, the existing nickel-aluminum composite material generally has the problems of easy inactivation or poor activity and the like. The nickel-aluminum composite material containing nickel carbide is obtained through research, and due to the fact that transition metal carbide has the advantages of being high in catalytic activity, low in price, stable in performance, resistant to poisoning and the like, the catalytic activity is effectively improved due to the synergistic effect of nickel carbide and nickel in the composite material.
According to the invention, the X-ray photoelectron spectroscopy (XPS) spectrum of the nickel-aluminum composite material contains the peaks of nickel (Ni), aluminum (Al), carbon (C) and oxygen (O). Analyzed to contain 3 Ni2p 3/2 The corresponding binding energies of the peaks are respectively 854.0 eV-854.2 eV, 856.3 eV-856.5 eV and 859.1 eV-859.3 eV.
According to the present invention, in some embodiments, the nickel aluminum composite has a surface nickel element content of 1mol% to 4mol%, a surface aluminum element content of 40mol% to 55mol%, a surface carbon element content of 17mol% to 25mol%, and a surface oxygen element content of 30mol% to 42mol%, based on a total molar amount of surface elements of the nickel aluminum composite determined by XPS spectroscopy. According to the invention, by adjusting the component proportion, the catalytic oxidation activity is better when the proportion is reached.
According to the invention, the composite material is granular, the influence of the grain size of the granules on the catalytic effect is larger, and the larger the grain size is, the fewer the surface active sites are; the smaller the particle size, the easier it is for particles to be sintered at a lower temperature. Therefore, tests show that the particle size of the nickel phase in the nickel-aluminum composite material is 10 nm-80 nm.
The invention also provides a method for preparing the nickel-aluminum composite material containing nickel carbide, which comprises the following steps: s1: providing a nickel-aluminum precursor; s2: carrying out heating treatment on the nickel-aluminum precursor, and then carrying out hydrogen reduction treatment; s3: cooling the nickel-aluminum precursor subjected to hydrogen reduction treatment; s4: introducing a carbon source to carry out low-temperature vapor deposition on the nickel-aluminum precursor subjected to cooling treatment to obtain a nickel-aluminum composite material; wherein the temperature of the low-temperature vapor deposition is 200-300 ℃, and the deposition time is 30-1440 minutes.
In some embodiments, the nickel aluminum precursor has a hydrotalcite crystal structure, which may be prepared by coprecipitation and/or hydrothermal crystallization. Specifically, the nickel aluminum precursor may be prepared by, but is not limited to, the following method.
According to a specific embodiment of the present invention, the nickel aluminum precursor is prepared by a coprecipitation method, and the specific steps may include: simultaneously dropwise adding alkali liquor and aqueous solution containing trivalent aluminum salt and divalent nickel salt into water for precipitation treatment, so that trivalent aluminum salt and divalent nickel salt generate coprecipitate; the coprecipitate is aged. The feeding amount of the aqueous solution containing the trivalent aluminum salt and the divalent nickel salt can be controlled according to the nickel-aluminum content in the target carbon-coated nickel-aluminum composite material, and the adding amount of the alkali liquor is controlled according to the condition that the trivalent aluminum salt and the divalent nickel salt are completely precipitated. The simultaneous addition of the alkali solution, the trivalent aluminum salt and the divalent nickel salt to the water can improve the dispersion effect of the alkali solution, the aluminum salt and the nickel salt during the initial dropwise addition. In addition, the trivalent aluminum salt and the divalent nickel salt are not particularly limited as long as they are soluble in water, and the alkali in the alkali solution is not particularly limited as long as they are capable of precipitating the trivalent aluminum salt and the divalent nickel salt, for example, the trivalent aluminum salt may include aluminum nitrate and/or aluminum chloride, the divalent nickel salt may include nickel nitrate and/or nickel chloride, and the molar ratio of aluminum in the trivalent aluminum salt to nickel in the divalent nickel salt may be 1: (2-4), the molar concentration of the trivalent aluminum salt can be 0.3-0.6 mol/L; the alkali liquor can be an aqueous solution containing sodium hydroxide and sodium carbonate, the concentration of the sodium hydroxide in the alkali liquor can be 0.2-4 mol/L, and the concentration of the sodium carbonate can be 0.1-2 mol/L; the ratio of the number of moles of sodium hydroxide to the total number of moles of aluminum and nickel in the trivalent aluminum salt and the divalent nickel salt may be (2-4): the ratio of the number of moles of sodium carbonate to the total number of moles of aluminum and nickel in the trivalent aluminum salt and the divalent nickel salt may be (0.5-2): 1.
according to the invention, the precipitation treatment refers to a process of generating a precipitate from trivalent aluminum salt and divalent nickel salt by using an alkali solution, wherein the alkali solution can be mixed with the trivalent aluminum salt and the divalent nickel salt in various ways such as dripping, pumping or pouring. The aging treatment refers to further reacting the precipitate generated by the precipitation treatment to obtain the nickel-aluminum hydrotalcite crystal. The steps of the precipitation treatment and the aging treatment are not particularly limited, and only a nickel-aluminum precursor is obtained, for example, the conditions of the precipitation treatment may include: the temperature may be from room temperature to less than 100 ℃, preferably from 40 ℃ to less than 100 ℃, more preferably from 50 ℃ to less than 90 ℃ to increase the speed of the precipitation process. After the dropwise addition is started, the nickel ions and the aluminum ions are controlled to precipitate under the condition that the pH value is more than 7, preferably between 8 and 9, and the specific operation can be as follows: controlling the pH value of the aqueous solution to be between 8 and 9 through the dropping speed of the alkali liquor, accelerating the dropping speed of the alkali liquor if the pH value is lower than 8, and slowing the dropping speed of the alkali liquor if the pH value is higher than 9; the aging treatment conditions may include: the temperature is 40 ℃ to less than 100 ℃ and the time is 2 to 72 hours, preferably 6 to 72 hours, more preferably 24 to 48 hours. The nickel-aluminum hydrotalcite crystal obtained by aging treatment can be further washed to be neutral and dried to obtain a nickel-aluminum precursor.
According to the invention, after the nickel-aluminum precursor is obtained, the method also comprises the step of heating the nickel-aluminum precursor to reach the temperature of high-temperature hydrogen reduction treatment. The high-temperature hydrogen reduction treatment has the following effects: on one hand, a nickel-aluminum precursor existing in a hydroxide (hydrotalcite) form is dehydrated and decomposed to generate nickel-aluminum oxide, and on the other hand, the generated nickel-aluminum oxide is reduced to generate simple substance nickel as an active center. The conditions of the hydrogen reduction treatment may include: the temperature is 500-900 ℃, the time is 30-180 minutes, preferably 61-90 minutes, and the hydrogen flow is 51-200 ml/(min. G nickel-aluminum precursor). The hydrogen reduction treatment conditions are favorable for completely reducing nickel in the composite material, and the nickel oxidized in the composite material cannot be completely reduced due to too short treatment time or too low hydrogen flow rate, so that the catalytic performance of the composite material is reduced.
In some embodiments, the foregoing steps S2 and S3 may be performed with the first protective gas being introduced, that is, the nickel-aluminum precursor may be heated and heat-treated with the first protective gas until the temperature reaches the temperature of the hydrogen reduction treatment, and then the nickel-aluminum precursor after the high-temperature hydrogen reduction treatment is cooled to the temperature of the low-temperature carbon deposition with the protective gas being introduced. Wherein, the first protective gas can be nitrogen and/or argon, and the flow rate of the first protective gas is 10-500 ml/(min. G nickel-aluminum precursor), but is not limited thereto; the introduced first protective gas is used as a carrier gas in the temperature rise process of the nickel-aluminum precursor, so that the danger caused by the fact that the nickel-aluminum precursor is not contacted with air when the hydrogen reduction reaction is carried out can be ensured.
In some embodiments, the speed of the temperature-raising heat treatment is 1-5 ℃/min, the temperature-raising speed is not too fast, and the nickel-aluminum precursor is heated uniformly by slowly raising the temperature; the temperature reduction rate may be slightly higher than the temperature increase rate, but not too high, and the temperature reduction treatment rate is preferably 5 to 20 ℃/min.
According to the invention, the nickel-aluminum precursor subjected to temperature reduction treatment is subjected to low-temperature vapor deposition. Specifically, in the low-temperature vapor deposition process, after the nickel-aluminum precursor is cooled to a certain temperature, a carbon source is introduced to perform low-temperature vapor deposition. In some embodiments, the carbon source can be an alcohol species in the liquid phase, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, or tert-butanol, more preferably ethanol.
According to the invention, the step of introducing the carbon source comprises the following steps: introducing a second protective gas into the alcohol substance, and contacting the alcohol substance with the cooled nickel-aluminum precursor by a bubbling carrier gas method; wherein the alcohol substance needs to be heated and kept warm. Specifically, the alcohol substance can be placed in a heat-insulating gas washing device, the second protective gas enters the heat-insulating gas washing device through a gas path, and the liquid alcohol substance is loaded into the deposition reaction chamber in a gas form through a bubbling method to perform a vapor deposition reaction. In a specific experimental process, the flow rate of the second protective gas and the heat preservation temperature of the alcohol substance can be changed to control the rate of the carbon source entering the reactor. Through a large number of experiments, the heat preservation temperature of the alcohols is preferably kept between 30 and 90 ℃, and if the heat preservation temperature is too low, the saturated vapor pressure of the liquid phase alcohols is too low, and the carbon source gas blown into the tubular furnace is too little, so that the reaction rate is too low and even difficult to perform; when the heat preservation temperature is too high, too much carbon source gas is blown into the tubular furnace, the reaction rate is too high, carbon deposition is easy to generate, and alcohol substances are likely to undergo organic chemical reactions such as condensation at higher temperature (particularly, the boiling point of ethanol is lower, and when the ethanol is used as a carbon source, the heat preservation temperature is kept at 30-60 ℃); the second protective gas may be nitrogen and/or argon, and the flow rate of the second protective gas is 10 to 500 ml/(min. G nickel-aluminum precursor), but is not limited thereto.
By the method, a carbon source reacts with the elemental nickel nanoparticles subjected to hydrogen reduction treatment, so that part of nickel can form nickel carbide. Research shows that at higher deposition temperature, nickel carbide will decompose to form graphite carbon coated metal nickel nanoparticles or to form carbon nano-rods, while at lower temperature the above-mentioned vapor deposition reaction cannot take place. A large number of experiments show that the conditions of the low-temperature vapor deposition reaction for generating the nickel-aluminum composite material containing nickel carbide are as follows: the temperature is 200-300 ℃, and the time is 30-1440 minutes. Preferably, the temperature is 225 to 275 ℃ and the time is 60 to 180 minutes.
The invention also provides the application of the nickel-aluminum composite material in catalytic oxidation of industrial waste gas, which comprises the following steps: the nickel-aluminum composite material is used as a catalyst to contact with industrial waste gas for catalytic oxidation reaction, wherein the industrial waste gas is the waste gas generated in the production process for preparing maleic anhydride by industrial n-butane oxidation.
According to one embodiment of the invention, the catalytic oxidation reaction is carried out at a temperature of 200-500 ℃, and the reaction space velocity is 2000-5000 ml industrial waste gas/(h.g nickel-aluminum composite material); the butane accounts for 0.01 to 2 volume percent of the content of the industrial waste gas in percentage by volume. The composite material of the invention can be used as a catalyst to obtain good reaction effect under the condition of reducing reaction severity, such as reducing reaction temperature, increasing space velocity and the like. Preferably, the nickel-aluminum composite material can be used for completely catalytically oxidizing butane components with the content of 0.012 to 2 volume percent in waste gas generated in a maleic anhydride production process into CO at 350 DEG C 2 The elimination rate can reach more than 95 percent by volume, and the butane component can be completely catalyzed and oxidized into CO at 400 DEG C 2 . Therefore, the nickel-aluminum composite material has good catalytic activity in catalytic oxidation reaction.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, all reagents used in the invention are analytically pure.
The model of the XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, K α ray (wavelength λ =0.154 nm), tube voltage 40kV, tube current 200mA, scanning speed 10 ° (2 θ)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Nippon electronics Co., ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV.
The X-ray photoelectron spectrum analyzer (XPS) adopted by the invention is an ESCALb 220i-XL type ray photoelectron analyzer which is produced by VG scientific corporation and is provided with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test -9 mbar。
Example 1
(1) Preparation of nickel-aluminum precursor
Weighing 23.28g (0.08 mol) of nickel nitrate hexahydrate and 15.00g (0.04 mol) of aluminum nitrate nonahydrate and 240mL of deionized water to prepare a mixed salt solution, adding 10.80g (0.27 mol) of sodium hydroxide and 10.16g (0.096 mol) of anhydrous sodium carbonate and 240mL of deionized water to prepare a mixed alkali solution, simultaneously dropwise adding the two mixed solutions into a 1000mL three-neck flask which is pre-filled with deionized water and has the constant temperature of 60 ℃ and 300mL of deionized water, stirring simultaneously, strictly controlling the pH =8.5 (namely controlling the pH between 8.4 and 8.6) of the precipitate of trivalent aluminum salt and divalent nickel salt in the three-neck flask, heating to 80 ℃ after dropwise adding, aging for 24 hours, centrifugally washing to be neutral, and drying in a blast drying box at 60 ℃ to obtain the high-dispersion nickel-aluminum precursor.
(2) Preparation of nickel-aluminum composite material
Weighing 1.0g of nickel-aluminum precursor NiAl-1, placing the nickel-aluminum precursor NiAl-1 in a porcelain boat, then placing the porcelain boat in a tubular furnace in a nitrogen protection atmosphere, carrying out temperature programming at 5 ℃/min at a nitrogen flow of 100mL/min, and heating to 800 ℃; keeping the flow of nitrogen unchanged, maintaining the temperature of the tube furnace at 800 ℃ for high-temperature hydrogen reduction treatment, introducing 100mL/min of hydrogen for 61min, and closing the hydrogen; performing a programmed cooling process at 10 ℃/min, and reducing the temperature to 250 ℃; keeping the nitrogen flow unchanged, maintaining the temperature of the tubular furnace at 250 ℃ for low-temperature vapor deposition treatment, adding a heat-preservation gas washing device filled with ethanol into a gas path, introducing the ethanol by a bubbling method, keeping the heat preservation temperature of the ethanol at 50 ℃, reacting for 180 minutes, withdrawing the gas washing device after the reaction is finished, keeping the nitrogen flow unchanged, and naturally cooling to room temperature to obtain the nickel-aluminum composite material containing nickel carbide.
Fig. 1 is an X-ray diffraction pattern (XRD) of the nickel aluminum composite material, wherein the abscissa is an angle of 2 θ in units, and the ordinate is intensity (intensity); FIG. 2 and FIG. 3 are high-power transmission electron micrographs (HRTEM) of the nickel-aluminum composite material at different magnifications, respectively; FIG. 4 is an XPS spectrum of the nickel on the surface of the nickel-aluminum composite material; the surface element molar content of the nickel-aluminum composite material determined by XPS spectrogram is shown in Table 1.
As can be seen from FIG. 1, the nickel-aluminum composite material of example 1 contains elemental nickel Ni and nickel carbide Ni 3 Characteristic peak of C. As can be seen from FIG. 2, the morphology of the composite material is characterized by nickel phases (elemental Ni and Ni carbide) 3 C) The nickel phase nano particles are loaded on alumina in the form of nano particles, and the particle size of the nickel phase nano particles is about 10nm to 80nm. In FIG. 1, there is no peak characteristic to alumina, indicating that alumina exists in an amorphous form. As can be seen from FIG. 3, ni is present on the surface of the composite material 0 、Ni 2+ 、Ni 3+ The XPS spectrum peaks of (1) are respectively positioned at 854.10eV, 856.43eV and 859.24eV. From the peak area, the surface Ni can be calculated 0 The atomic ratio of all Ni phases is:
A Ni 0 /(A Ni 0 +A Ni 2+ +A Ni 3+ +A Nisat. )＝28.6％
example 2
A nickel aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the low-temperature vapor deposition temperature was 275 ℃. XPS elemental composition data for the prepared nickel-aluminum composite containing nickel carbide is shown in Table 1.
Example 3
A nickel aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the low-temperature vapor deposition temperature was 225 ℃. XPS elemental composition data for the prepared nickel-aluminum composite containing nickel carbide is shown in Table 1.
Example 4
A nickel-aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the temperature of the ethanol was kept at 40 ℃ during the low-temperature vapor deposition. XPS elemental composition data for the prepared nickel-aluminum composite containing nickel carbide is shown in Table 1.
Example 5
A nickel-aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the temperature of the ethanol was maintained at 60 ℃ during the low-temperature vapor deposition. XPS element composition data of the prepared nickel-aluminum composite material are shown in a table 1.
Example 6
A nickel aluminum composite material containing nickel carbide was prepared in the same manner as in example 1, except that, in the step (2), the flow rate of nitrogen gas during the low-temperature vapor deposition was 50mL/min. The XPS element composition data of the prepared nickel-aluminum composite material are shown in the table 1.
Example 7
A nickel aluminum composite material containing nickel carbide was prepared in the same manner as in example 1, except that, in the step (2), the flow rate of nitrogen gas during the low-temperature vapor deposition was 400mL/min. The XPS element composition data of the prepared nickel-aluminum composite material are shown in the table 1.
Comparative example 1
A nickel aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the low-temperature vapor deposition temperature was 400 ℃. An X-ray diffraction pattern (XRD) of the nickel aluminum composite material of comparative example 1 is shown in fig. 5, an HRTEM of the nickel aluminum composite material of comparative example 1 is shown in fig. 6, and the surface element molar content of the nickel aluminum composite material of comparative example 1 determined by the XPS spectrum is shown in table 1.
As can be seen from FIG. 5, the nickel-aluminum composite material of comparative example 1 contains characteristic peaks of elemental nickel Ni without containing nickel carbide Ni 3 Characteristic peak of C. As can be seen from fig. 6, the morphological characteristics of the nickel-aluminum composite material are that the elemental nickel is loaded on the alumina in the form of nanoparticles, and more nano carbon rods grow on the nickel nanoparticles, which can be mutually verified from the characteristic peaks of graphite C existing in fig. 5. The composite material in fig. 5 does not have the characteristic peak of alumina, indicating that alumina exists in an amorphous form.
Comparative example 2
A nickel aluminum composite material was prepared in the same manner as in example 1, except that, in the step (2), the low temperature vapor deposition temperature was 350 ℃. The X-ray diffraction pattern (XRD) of the nickel aluminum composite material of comparative example 2 is shown in fig. 5, the HRTEM of the nickel aluminum composite material of comparative example 2 is shown in fig. 7, and the surface element molar content of the nickel aluminum composite material of comparative example 2 determined by the XPS spectrum is shown in table 1.
As can be seen from FIG. 5, the composite material of comparative example 2 contains the characteristic peak of elemental nickel Ni without nickel carbide Ni 3 Characteristic peak of C. As can be seen from fig. 7, the morphology of the composite material is characterized by graphitic carbon-coated nickel nanoparticles supported on alumina, and the composite material in fig. 5 does not have the characteristic peaks of alumina, indicating that alumina exists in an amorphous form.
TABLE 1
Test example
The nickel-aluminum composite materials of examples 1 to 7 and comparative examples 1 and 2 were used as catalysts in experiments for complete catalytic elimination of butane from exhaust gas generated in a process for producing maleic anhydride by oxidation of n-butane in industry, and evaluation of butane elimination rate of the catalytic materials was performed, and under the same conditions, the higher the butane elimination rate, the higher the catalyst activity. The specific evaluation method comprises the following steps:
sending the collected butane-containing maleic anhydride production process waste gas into a fixed bed reactor loaded with a composite material to contact with the composite material serving as a catalyst for catalytic oxidation reaction, performing gas chromatography analysis on the obtained reaction product, and calculating the butane elimination rate, wherein the butane elimination rate =100% -the butane volume in the reaction product/the butane volume in the maleic anhydride production process waste gas is multiplied by 100%.
The process off-gas from the maleic anhydride production contained about 1% by volume of butane, the balance air and very small amounts of carbon monoxide and carbon dioxide, the reaction space velocity was 5000 ml of industrial off-gas/(hr. G catalyst), the evaluation time was 5 hours, and the butane elimination rate and the temperature required for complete butane elimination at 350 ℃ are shown in table 2.
TABLE 2
As can be seen from tables 1 and 2, the nickel-aluminum composite material containing nickel carbide has better butane catalytic elimination performance compared with carbon nano-rods and carbon-coated elemental nickel materials, the butane elimination rate in the waste gas of the maleic anhydride production process containing 1 volume percent of butane can reach more than 90 percent at 350 ℃, and butane can be completely catalytically oxidized into CO at the temperature lower than 400 DEG C 2 The composites of comparative examples 1 and 2, on the other hand, are able to completely catalyze the oxidation of butane to CO at least at 500 ℃ as catalysts 2 。
In addition, as can be seen from tables 1 and 2, in the nickel-aluminum composite material containing nickel carbide (examples 1 to 7), the higher the low-temperature vapor deposition temperature, the larger the carbon source gas flow rate, the larger the bubbling carrier gas flow rate, or the higher the carbon source holding temperature, the lower the surface Ni element content, the higher the surface C element content, and the surface Ni 0 The lower the proportional content, the better the catalytic performance of the composite. It is believed that the higher the nickel carbide content on the surface of the composite material, the better the catalytic performance. Nickel carbide is an important component for improving the catalytic performance of the composite material.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (18)
1. The nickel-aluminum composite material is characterized by comprising aluminum oxide, nickel carbide and simple substance nickel;
the preparation method of the nickel-aluminum composite material comprises the following steps:
s1: providing a nickel-aluminum precursor;
s2: carrying out heating treatment on the nickel-aluminum precursor, and then carrying out hydrogen reduction treatment;
s3: cooling the nickel-aluminum precursor subjected to hydrogen reduction treatment;
s4: introducing a carbon source to carry out low-temperature vapor deposition on the nickel-aluminum precursor subjected to the cooling treatment to obtain the nickel-aluminum composite material;
wherein the temperature of the low-temperature vapor deposition is 200-300 ℃, and the deposition time is 30-1440 minutes.
2. The nickel aluminium composite of claim 1, wherein the nickel aluminium composite has an XPS spectrum comprising 3 Ni2p 3/2 The corresponding binding energies of the peaks are 854.0 eV-854.2 eV, 856.3 eV-856.5 eV, 859.1 eV-859.3 eV.
3. The nickel-aluminum composite material of claim 1, wherein the nickel-aluminum composite material has a surface nickel element content of 0.5mol% to 4mol%, a surface aluminum element content of 30mol% to 55mol%, a surface carbon element content of 13mol% to 30mol%, and a surface oxygen element content of 30mol% to 42mol%, based on the total surface element molar amount of the nickel-aluminum composite material determined by XPS spectroscopy.
4. The nickel-aluminum composite material according to claim 1, wherein the particle size of the nickel phase in the nickel-aluminum composite material is 10nm to 80nm.
5. A method of making the nickel aluminium composite material of any one of claims 1~4 comprising the steps of:
s1: providing a nickel-aluminum precursor;
s2: carrying out heating treatment on the nickel-aluminum precursor, and then carrying out hydrogen reduction treatment;
s3: cooling the nickel-aluminum precursor subjected to hydrogen reduction treatment;
s4: introducing a carbon source to carry out low-temperature vapor deposition on the nickel-aluminum precursor subjected to the cooling treatment to obtain the nickel-aluminum composite material;
wherein the temperature of the low-temperature vapor deposition is 200-300 ℃, and the deposition time is 30-1440 minutes.
6. The method according to claim 5, wherein step S2 and/or step S3 is performed in the presence of a first protective gas.
7. The method according to claim 6, wherein the first protective gas is nitrogen and/or argon, and the flow rate of the first protective gas is 10 to 500 ml/(min. G of nickel-aluminum precursor).
8. The method according to claim 5, wherein the carbon source is an alcohol.
9. The method according to claim 8, wherein the carbon source is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, or tert-butanol.
10. The method according to claim 9, wherein the carbon source is ethanol.
11. The method according to claim 8, wherein the step of introducing a carbon source comprises:
introducing a second protective gas into the alcohol substance, and contacting the alcohol substance with the nickel-aluminum precursor subjected to temperature reduction treatment by a bubbling carrier gas method; wherein the temperature of the alcohol substance is kept between 30 and 90 ℃.
12. The method according to claim 11, wherein the second protective gas is nitrogen and/or argon, and the flow rate of the second protective gas is 10 to 500 ml/(min. G of the nickel-aluminum precursor).
13. The production method according to claim 5, wherein a temperature rise rate in the temperature rise heat treatment is 1 ℃/min to 5 ℃/min, and a temperature fall rate in the temperature fall heat treatment is 5 ℃/min to 20 ℃/min.
14. The preparation method according to claim 5, wherein the hydrogen reduction treatment comprises contacting the nickel-aluminum precursor subjected to the temperature-raising heat treatment with hydrogen gas, wherein the temperature of the hydrogen reduction treatment is 500 to 900 ℃; the time is 61 minutes to 180 minutes; the hydrogen flow is 51-200 ml/(min. G nickel-aluminum precursor).
15. The method according to claim 14, wherein the hydrogen reduction treatment is performed for 61 to 90 minutes.
16. The method according to claim 5, wherein the structure of the nickel aluminum precursor is a hydrotalcite crystal structure.
17. Use of the nickel alumina composite of any of claims 1~4 in the catalytic oxidation of industrial waste gas comprising: the nickel-aluminum composite material is used as a catalyst to contact with industrial waste gas for catalytic oxidation reaction, wherein the industrial waste gas is the waste gas generated in the production process of preparing maleic anhydride by oxidizing industrial n-butane.
18. The use according to claim 17, wherein the catalytic oxidation reaction is carried out at a temperature of 200 ℃ to 500 ℃ and a reaction space velocity of 2000 to 5000 ml of industrial waste gas/(hr. G of nickel-aluminum composite); the butane accounts for 0.01-2% of the industrial waste gas content in volume percentage.
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| CN104176941A (en) * | 2014-08-18 | 2014-12-03 | 苏州新协力环保科技有限公司 | Novel hermetically-coated optical fiber |
| CN108856706A (en) * | 2017-05-10 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of carbon-coating nickel aluminium composite material and its preparation method and application |
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