TWI718615B - Nickel included catalyst, use of the same as a catalyst of hydrogen production reaction, and the manufacturing method - Google Patents

Abstract

A nickel included catalyst, am use of the same as a catalyst of hydrogen production reaction, and the manufacturing method are provided. The nickel included catalyst includes a Ca-Ni-Al compound represented by Ca _xNi _1-xAl.The manufacturing method includes the steps of : (A1000) providing a calcium nitrate solution, a nickel nitrate solution, and an aluminum nitrate solution; (A2000) mixing the calcium nitrate solution, the nickel nitrate solution, and the aluminum nitrate solution and stirring with basic liquid to form a Ca-Ni-Al mixing solution; (A300) filtrating, drying and incinerating the Ca-Ni-Al mixing solution to obtain a Ca-Ni-Al compound as a nickel included catalyst.

Description

Nickel-based catalyst, its use as a catalyst for hydrogen production reaction, and manufacturing method

The present invention relates to a nickel-based catalyst.

Existing ethanol steam reforming hydrogen production technology, such as adding adsorbent catalyst circuit steam reforming, the hydrogen production performance is mainly determined by the material. As a result, if the hydrogen content is not high, it will affect the subsequent purification system load and increase the oxygen consumption.

The use of nickel catalysts for ethanol recombination to produce hydrogen is usually prone to carbon deposits at 600°C, which is not conducive to the continuation of the reaction and there is room for improvement.

The object of the present invention is to provide a nickel-based catalyst, its use as a catalyst for a hydrogen production reaction, and a manufacturing method that can efficiently generate hydrogen.

The nickel-based catalyst of the present invention includes nickel, calcium, and aluminum.

In the embodiment of the present invention, the nickel-based catalyst includes a calcium nickel aluminum compound, represented by the following formula (I), Ca _x Ni _1-x Al formula (I).

In the embodiment of the present invention, x=0.80~0.94.

In the embodiment of the present invention, the nickel-based catalyst includes nickel-based alumina (Ni/Al ₂ O ₃ ) and calcium aluminum compound (Ca-Al-CO ₃ ).

In the embodiment of the present invention, the weight ratio of the nickel-based alumina and the calcium-aluminum compound is 1:4.

In the embodiment of the present invention, the nickel-based alumina is a powder with a diameter of 10-50 um, and the calcium-aluminum compound is a powder with a diameter of 100-400 nm.

The nickel-based catalyst manufacturing method of the present invention includes the following steps in sequence: (A1000) providing calcium nitrate, nickel nitrate, and aluminum nitrate solutions; (A2000) mixing the calcium nitrate, nickel nitrate, and aluminum nitrate solutions with lye Stir to form a calcium-nickel-aluminum mixed solution; (A3000) filter, dry, and calcinate the calcium-nickel-aluminum mixed solution to obtain a calcium-nickel-aluminum compound as a nickel-based catalyst.

In an embodiment of the present invention, step A1000 includes providing the molar ratio of calcium in calcium nitrate, nickel in nickel nitrate, and aluminum in aluminum nitrate to 7:1:1. The calcium nickel aluminum compound is represented by the following formula (I), and Ca _x Ni _1-x Al is the formula (I). Where x=0.80~0.94.

In the embodiment of the present invention, the nickel-based catalyst manufacturing method sequentially includes the following steps: (B1000) providing nickel nitrate crystals; (B2000) dissolving nickel nitrate crystals to form a nickel nitrate solution; (B3000) in a nickel nitrate solution Add porous alumina powder and mix and stir uniformly to form an alumina-containing suspension solution; (B4000) filter and dry the alumina-containing suspension solution to obtain nickel-based alumina catalyst precursor powder; (B5000) oxidize the above-mentioned nickel-based catalyst The aluminum catalyst precursor powder is calcined to obtain the nickel-based alumina (Ni/Al ₂ O ₃ ) catalyst powder; (B6000) the nickel-based alumina catalyst powder and the calcium-aluminum compound powder are mixed in a weight ratio of 1:4, After adding water and grinding, it is extruded into pellets and calcined to form a nickel-based catalyst.

Fig. 1 is a schematic flow diagram of an embodiment of the method for manufacturing a nickel-based catalyst of the present invention.

Fig. 2 is a schematic flow diagram of different embodiments of the method for manufacturing a nickel-based catalyst of the present invention.

Figure 3 shows the results of the CO _{2 capture test.}

The nickel-based catalyst of the present invention includes nickel, calcium, and aluminum. More specifically, in one embodiment, the nickel-based catalyst includes a calcium nickel aluminum compound, represented by the following formula (I), Ca _x Ni _1-x Al formula (I).

Wherein, x=0.80~0.94, preferably 0.87.

In one embodiment, a calcium-nickel-aluminum molar ratio of 7:1:1 calcium-nickel-aluminum compound is synthesized by the co-precipitation method, and calcium nitrate, nickel nitrate, and aluminum nitrate solutions are prepared in the above-mentioned ratio, and the mixture is stirred with lye to form The mixed solution is filtered, dried and calcined to obtain calcium nickel aluminum compound (Ca _x Ni _1-x Al) powder.

Furthermore, as shown in the schematic flow chart shown in FIG. 1, the manufacturing method of the aforementioned nickel-based catalyst containing a calcium-nickel-aluminum compound sequentially includes, for example, the following steps.

In step A1000, calcium nitrate, nickel nitrate, and aluminum nitrate solutions are provided. More specifically, in a preferred embodiment, this step includes providing a molar ratio of calcium in calcium nitrate, nickel in nickel nitrate, and aluminum in aluminum nitrate at 7:1:1.

In step A2000, the calcium nitrate, nickel nitrate, and aluminum nitrate solutions are mixed and then stirred with lye such as sodium hydroxide solution to form a calcium, nickel, and aluminum mixed solution.

In step A3000, the calcium-nickel-aluminum mixed solution is filtered, dried, and calcined to obtain a calcium-nickel-aluminum compound as a nickel-based catalyst. On the other hand, the calcium-nickel-aluminum compound can be further added with water and ground, and then extruded into long particles with a width of 2 to 3 mm, and calcined at 750°C for 6 hours to become nickel-based catalyst particles. Among them, the calcium nickel aluminum compound is represented by the following formula (I), and Ca _x Ni _1-x Al is the formula (I).

In various embodiments, the nickel-based catalyst includes nickel-based alumina (Ni/Al ₂ O ₃ ) catalyst powder and calcium aluminum compound (Ca-Al-CO ₃ ) powder. The weight ratio of the nickel-based alumina catalyst powder and the calcium-aluminum compound powder is preferably 1:4. The preferred size of the nickel-based alumina catalyst powder is 10-50um, and the preferred size of the calcium-aluminum compound powder is 100-400nm.

In one embodiment, after dissolving a certain amount of nickel nitrate crystals, it is mixed with porous alumina balls (3~5mm) and stirred for 24 hours, filtered, dried and calcined to obtain nickel-based alumina (Ni/Al ₂ O ₃ ) Particles (3~5mm). In addition, the nickel-based alumina (Ni/Al ₂ O ₃ ) powder was prepared by the same method as the above, and it was mixed with the calcium-aluminum compound powder in a weight ratio of 1:4, and then calcined (750°C/6 hours) Then to form a nickel-based catalyst.

Furthermore, as shown in the schematic flow chart shown in FIG. 2, the manufacturing method of the nickel-based catalyst including nickel-based alumina catalyst powder and calcium-aluminum compound powder includes, for example, the following steps in sequence.

Step B1000, providing nickel nitrate crystals.

Step B2000, dissolving nickel nitrate crystals to form a nickel nitrate solution.

In step B3000, the porous alumina powder is added to the nickel nitrate solution and mixed evenly to form an alumina-containing suspension solution.

Step B4000, filtering the alumina-containing suspension solution to obtain a nickel-based alumina catalyst precursor.

In step B5000, the nickel-based alumina catalyst precursor is dried and then calcined at 600° C. for 4 hours to obtain nickel-based alumina (Ni/Al ₂ O ₃ ) catalyst powder.

In step B6000, the nickel-based alumina catalyst powder and the calcium-aluminum compound powder are mixed in a weight ratio of 1:4, and after adding water and grinding, extruding the long and wide particles of 2~3mm, calcining at 750°C for 6 hours Then become nickel-based catalyst particles.

The following is a further test for the nickel-based catalyst of the present invention. Among them, Comparative Example 1 is nickel-based alumina catalyst particles. The preparation method is to add alumina balls to the nickel nitrate solution and mix for 24 hours, filter and dry, and then calcinate at 600°C for 4 hours to obtain nickel-based alumina catalyst. Medium particles (3~5mm). Comparative example 2 is that nickel-based alumina catalyst powder (Ni/Al ₂ O ₃ ) and calcium oxide powder are uniformly mixed in a weight ratio of 1:4, and water is added and ground, and then extruded and granulated into 2~3mm particles, and then subjected to 750 mm. After calcination at ℃ for 6 hours, recombined mixed calcium oxide (CaO) nickel-based catalyst particles were obtained. Example 1 is that the nickel-based alumina catalyst powder (Ni/Al ₂ O ₃ ) and the calcium-aluminum compound powder are uniformly mixed in a weight ratio of 1:4, and water is added and ground, and then extruded and granulated into 2~3mm particles. After calcination at 750°C for 6 hours, the nickel-based catalyst particles were obtained. Example 2 is calcium nickel aluminum compound Ca _0.87 Ni _0.13 Al particles. Among them, after fluorescence analysis (X-ray tube vol.: 50kV; instrument brand: HORIBA, MESA 50), the chemical composition of the material is shown in Table 1.

_{A total of 50 CO 2} capture tests (TGA, NETZSCH, STA-449F3) were performed on the above-mentioned comparative examples and examples at 600-750° C. for 50 hours, and the results are shown in FIG. 3. Among them, the carbon capture conversion rate of the present invention in Example 1 is about 44%, which is 95% stable compared with the initial conversion rate, and the carbon capture conversion rate of the present invention in Example 2 is about 47%, which is comparable to the initial conversion rate. Up to 92% stability. Accordingly, the nickel-based catalyst of the present invention has high CO ₂ capture capacity and stability.

The above comparative examples and examples are placed in a self-developed recombination reactor, the inlet is fed with a 40% ethanol aqueous solution as the recombination hydrogen source, the gas generated by the evaporator enters the reactor for 600℃ steam recombination reaction, and the outlet is condensed and dried , The composition of reconstituted steam obtained by online analyzer (MRU, Vario plus) is shown in Table 2.

It can be seen from Table 2 that the recombinant hydrogen concentration of Example 1 is higher than 95% and the CO drops to >1.0%, and the recombinant hydrogen concentration of Example 2 is higher than 98%, and the CO drops to >0.1%. Accordingly, the use of the nickel-based catalyst of the present invention as a catalyst for a hydrogen production reaction can efficiently generate hydrogen gas. In addition, it is beneficial to the back-end gas purification system load and fuel cell applications.

A1000: steps A1000: steps A3000: Steps B1000: steps B2000: steps B3000: steps B4000: steps B5000: steps B6000: steps

Fig. 1 is a schematic flow diagram of an embodiment of the method for manufacturing a nickel-based catalyst of the present invention.

Fig. 2 is a schematic flow diagram of different embodiments of the method for manufacturing a nickel-based catalyst of the present invention.

Figure 3 shows the results of the CO _{2 capture test.}

(no)

A1000: steps

A2000: steps

A3000: Steps

Claims (6)

A nickel-based catalyst comprising nickel, calcium, and aluminum, wherein the nickel-based catalyst comprises a calcium-nickel-aluminum compound, represented by the following formula (I), Ca _x Ni _1-x Al formula (I); where x=0.80 ~0.94. A nickel-based catalyst, comprising: nickel-based alumina (Ni/Al ₂ O ₃ ); and calcium-aluminum compound (Ca-Al-CO ₃ ); wherein the weight ratio of the nickel-based alumina and the calcium-aluminum compound is 1 : 4. The nickel-based catalyst according to claim 2, wherein the nickel-based alumina is a powder of 10-50um, and the calcium-aluminum compound is a powder of 100-400nm. A use of the nickel-based catalyst according to any one of claims 1 to 3 as a catalyst for hydrogen production reaction from ethanol. A nickel-based catalyst manufacturing method, including the following steps in sequence: (A1000) providing calcium nitrate, nickel nitrate, and aluminum nitrate solutions, wherein the calcium in the calcium nitrate, the nickel in the nickel nitrate, and the aluminum in the aluminum nitrate The molar ratio is 7:1:1; (A2000) the calcium nitrate, the nickel nitrate, and the aluminum nitrate solution are mixed and then stirred with a sodium hydroxide solution to form a calcium-containing nickel-aluminum mixed solution; (A3000) the calcium-containing The nickel-aluminum mixed solution is filtered, dried, and calcined at 750°C for 6 hours to obtain a calcium-nickel-aluminum compound as a nickel-based catalyst. The method for manufacturing a nickel-based catalyst according to claim 5, wherein the calcium-nickel-aluminum compound after calcination is represented by the following formula (I): Ca _x Ni _1-x Al formula (I); wherein x=0.80~0.94.

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