CN1061269C - Ni-B amorphous alloy catalyst, its preparing process and application - Google Patents

Abstract

A supported catalyst composed of 0.1-30.0% by weight Ni-B amorphous alloy and 70.0-99.9% by weight of porous carrier material, the atomic ratio of Ni to B is 0.5-10.0, and the specific surface is 10-1000 ^m2 / The preparation method of the catalyst comprises feeding a nickel-containing porous carrier material with a molar concentration of 0.5 to 10.0 containing BH ₄ ^-solution at a concentration of 0.1 to 10.0 boron and nickel atoms at a temperature range from higher than the freezing point of the solution to 100°C than contact. The catalyst has high thermal stability and can be used in hydrogenation reactions of various compounds containing unsaturated functional groups.

Description

Preparation method and application of a nickel-boron amorphous alloy catalyst

The invention relates to an amorphous alloy catalyst, its preparation method and application, more specifically to an amorphous alloy catalyst containing nickel and boron, its preparation method and application.

In the study of amorphous alloy catalysts, the following two problems need to be solved: one is how to increase the specific surface area of amorphous alloy catalysts, and the other is how to keep the catalyst in the amorphous state during the catalytic process, that is, how to improve the surface area of the amorphous alloy catalyst. The thermal stability of alloy catalysts, in order to solve the above problems, many useful attempts have been made by the predecessors.

CN1073726A adopts the method of pre-alloying aluminum, rare earth, phosphorus and nickel or cobalt or iron, rapid quenching, and then removing the aluminum with sodium hydroxide to prepare a large specific surface Ni/Co/Fe-RE-P non- The crystalline alloy catalyst has a specific surface area of 50-130 m2 ^/ g, and its hydrogenation activity is higher than that of Raney Ni catalyst widely used in industry.

It was reported in Journal of Catalysis 150,434～438,1994 that 2.5MKBH ₄ aqueous solution was added dropwise to 0.1M nickel acetate ethanol solution at 25°C under stirring, and the precipitate was washed with 6 milliliters of 8M ammonia water and a large amount of distilled water successively to obtain a Amorphous Ni-B ultrafine particle catalyst, the specific surface of the catalyst can also reach 29.7 ^m2 /g, but the thermal stability of this Ni-B ultrafine particle is low.

In Applied Catalysis 37,339～343,1988, it was reported that Ni and P were deposited on silicon oxide by chemical plating) to prepare a Ni-P amorphous alloy catalyst loaded on silicon oxide. The specific surface of the catalyst can reach 85 m ² /g, and the supported Ni-P amorphous alloy catalyst not only has a larger specific surface, but also has improved thermal stability.

However, the results of the research on the preparation rules of the Ni-B amorphous alloy prepared by the chemical reduction method reported in J.Phys.Chem.97, 8504-8511, 1993 showed that the divalent metal ions and the reducing agent BH ₄ ^- The reaction in aqueous solution consists of three separate reactions as follows:

Since the above three reactions are very fast, if the carrier and the reaction solution are simply mixed together by electroless plating, it is difficult to ensure that the formed Ni-B amorphous alloy is loaded on the carrier, let alone Uniform dispersion of Ni-B amorphous alloy on a support. Due to the problem of loading technology, there is no report of supported Ni-B amorphous alloy so far.

One of purpose of the present invention is to provide a kind of Ni-B amorphous alloy catalyst with higher thermal stability and larger specific surface on the basis of prior art; Two of purpose of the present invention is to provide the preparation of this catalyst Method; The third object of the present invention is to provide the application of the catalyst in the hydrogenation reaction of compounds containing unsaturated functional groups.

The composition of the catalyst provided by the invention is: Ni-B amorphous alloy 0.1-30.0% by weight, porous carrier material 70.0-99.9% by weight, wherein the atomic ratio of Ni and B is 0.5-10.0.

The preparation method of the catalyst provided by the invention comprises mixing a nickel-containing porous carrier material with a solution containing BH ₄ ^-ions at a molar concentration of 0.5 to 10.0 in the range of 0.1 to 10.0 boron Nickel feed atomic ratio contact.

The application of the catalyst provided by the present invention refers to the application of the catalyst in the hydrogenation reaction of compounds containing unsaturated functional groups.

According to the catalyst provided by the invention, its preferred composition is 1.0-12.0% by weight of Ni-B amorphous alloy and 88.0-99.0% by weight of porous carrier material.

According to the catalyst provided by the present invention, the atomic ratio of nickel and boron is preferably 1.0-8.0.

According to the catalyst provided by the present invention, the porous carrier material refers to a non-oxidative porous carrier material, preferably one or more of porous inorganic oxides, activated carbon, zeolites, and molecular sieves; Oxides of Group IIA, IVB, VIB, IIIA, and IVA elements, among which one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, and calcium oxide are preferred; The zeolites and molecular sieves refer to various types of silica-alumina zeolites and heteroatom molecular sieves, such as A-type zeolite, X-type zeolite, Y-type zeolite, ZSM series zeolite, mordenite, Beta zeolite, Ω zeolite, phosphorus aluminum molecular sieve, titanium silicon Molecular sieves, etc.; preferred porous carrier materials are silica, alumina or activated carbon.

According to the catalyst provided by the present invention, its specific surface varies with the specific surface size of the carrier, and its specific surface can be 10-1000 ^m2 /g, preferably 100-1000 ^m2 /g.

According to the catalyzer provided by the invention, the active component nickel is all present with amorphous nickel, and at this moment, on the X-ray diffraction spectrum figure measured with CuKα target, there is a wider diffusion peak at 2θ=45 DEG C (as shown in Fig. 1 1), but as the load decreases, the diffusion peak becomes less and less obvious (as shown in 2-6 in Figure 1); in some cases, the peak shape of the diffusion peak is different due to different carriers Changes, such as when activated carbon is used as a carrier, the diffuse peak shape is sharper (as shown in Figure 2), and in other cases, the diffuse peak may be covered by the diffraction peak of the carrier at the same position (as shown in Figure 3 and Figure 4).

According to the preparation method of catalyst provided by the invention, concrete steps are as follows:

(1) impregnating the porous carrier material with a predetermined amount of soluble nickel salt solution, and then drying; or directly using a commercially available nickel-containing porous carrier material;

(2) Contact the nickel-containing porous carrier material with the BH ₄ ^- solution with a molar concentration of 0.5 to 10.0 within a temperature range from a temperature higher than the freezing point of the solution to 100°C, wherein the amount of BH ₄ ^- should be such that boron and nickel in the carrier The atomic ratio is 0.1 to 10.0;

(3) Wash the solid product with distilled water until there is no acid group.

Wherein, the nickel salt solution refers to an aqueous solution or an alcohol solution of a nickel salt, and the nickel salt is selected from one or more of nickel chloride, nickel sulfate, and soluble nickel carboxylate, preferably nickel chloride or nickel acetate.

The porous carrier material is preferably pre-dried at 90-200°C for more than 3 hours.

The nickel impregnation can use the impregnation method generally used in the preparation of the catalyst, preferably the saturated impregnation method.

The solution containing BH ₄ ^- ions refers to an aqueous solution or alcohol solution containing BH ₄ ^- , the precursor of the BH ₄ ^- ions is selected from KBH ₄ or NaBH ₄ or a mixture thereof, and the atomic ratio of boron to nickel is preferably 1.5 to 3.0 .

The contact of the nickel-containing porous carrier material with the BH ₄ ^-ion solution can be mixed directly, or the BH ₄ ^-ion- containing solution can be slowly added dropwise to the carrier material, preferably in a slow dropwise manner .

Although the temperature of the contact reaction can be set higher than 100°C, it is generally controlled within the range of higher than the freezing point of the solution to 100°C in order to save energy, preferably at room temperature to 50°C.

When the catalyst provided by the invention is used for the hydrogenation reaction of compounds containing unsaturated functional groups, the compounds containing unsaturated functional groups can be alkenes, alkynes, aromatic hydrocarbons, nitro compounds, carbonyl-containing compounds, carboxyl-containing compounds and nitriles. The hydrogenation reaction includes saturated hydrogenation reaction and selective hydrogenation reaction, especially the selective hydrogenation reaction of trace acetylene in ethylene. The process conditions for the hydrogenation reaction are the usual process conditions for each reaction.

Catalyst provided by the invention has the following advantages:

(1) The thermal stability of the catalyst is good, the catalyst provided by the invention has three phase transition peaks in the crystallization process, and its peak temperature is respectively 175, 280 and 362～445 ℃, and prior art (J.catal. 150,434～438,1994) the three phase transition peak temperatures of Ni-B amorphous ultrafine particles are only 144.1, 253.4 and 341.4°C respectively, which shows that the catalyst provided by the present invention has a higher temperature than that of Ni-B amorphous ultrafine particles. Higher thermal stability, it is easier to maintain its properties of amorphous alloy during the catalytic process.

(2) The specific surface of the catalyst changes with different ^supports , so the specific surface of the catalyst can be adjusted arbitrarily by using different supports. 29.7 m ² /g or so, the specific surface of the large surface Ni-RE-P amorphous alloy catalyst can only reach 130 m ² /g.

(3) catalytic activity is high, for example, the catalyzer of the load 4.19 weight %Ni-B amorphous alloy (wherein nickel content 3.97 weight %) provided by the invention, the Ni-La-P large surface amorphous alloy disclosed by CN1073726A When the catalyst and the traditional polycrystalline nickel catalyst containing 5% by weight of nickel are respectively used in the hydrogenation reaction of styrene at 60°C, the styrene conversion rate of the catalyst provided by the invention can reach 16.54% by weight, which is different from that of the unsupported Ni-La-P The large surface amorphous alloy catalyst (16.60% by weight of styrene conversion rate) is equivalent, while the styrene conversion rate is only 0.1% by weight when using polycrystalline nickel catalyst. This result shows that, on the one hand, the activity of the catalyst provided by the invention It is more than 165 times of the activity of traditional polycrystalline nickel catalysts. On the other hand, although the catalyst provided by the invention is quite active with the Ni-La-P large-surface amorphous alloy catalyst, the nickel content in the catalyst provided by the invention is only 3.97 wt. %, and the nickel content in the Ni-La-P large-surface amorphous alloy catalyst is as high as 87.4% by weight, which shows that the relative content of active nickel that catalyzes the reaction in the catalyst provided by the invention is much higher than that of Ni-La- P large-surface amorphous alloy catalyst, the catalyst provided by the invention is a low-nickel high-efficiency catalyst, which has incomparable advantages in the prior art.

The preparation method of the catalyst provided by the present invention abandons the traditional method of using BH ₄ ^- to reduce nickel in the solution, and first impregnates the nickel onto the porous carrier material, and then uses the solution containing BH ₄ ^- to reduce the nickel evenly dispersed on the porous carrier. Nickel in the material, the resulting Ni-B amorphous alloy can not only be loaded in the porous carrier material, but also the dispersion of the alloy in the carrier is relatively uniform, which is unmatched by the prior art, such as the electroless plating method.

Fig. 1 is the X-ray diffraction spectrogram of the Ni-B amorphous alloy catalyst of carrier with _SiO2 provided by the invention;

Fig. 2 is the X-ray diffraction spectrogram of the Ni-B amorphous alloy catalyst of carrier with gac provided by the present invention;

Fig. 3 is the X-ray diffraction spectrogram of the Ni-B amorphous alloy catalyst with δ-Al ₂ O ₃ as the carrier provided by the present invention;

Fig. 4 is the X-ray diffraction spectrogram of the Ni-B amorphous alloy catalyst provided by the present invention with γ-Al ₂ O ₃ as carrier;

Fig. 5 is provided by the invention with SiO ₂ is the different Ni, B content catalyst DSC curve of carrier;

Fig. 6 is a diagram showing the change of acetylene conversion rate with time when different catalysts catalyze the selective hydrogenation reaction of trace acetylene in ethylene.

The following examples will further illustrate the present invention, but do not limit the present invention thereby.

Examples 1-18

Preparation of the Ni-B amorphous alloy catalyst provided by the invention.

(1) carrier

Carrier 1 (code Z ₁ ) used is coarse-pore silica gel (produced by Qingdao Ocean Chemical Factory), carrier 2 (code Z ₂ ) is fine-pore silica gel (produced by Qingdao Ocean Chemical Factory), and carrier 3 (code Z ₃ ) is granular activated carbon (produced by Beijing Guanghua Timber Factory), carrier 4 (number Z ₄ ) is δ-alumina, which is spherical alumina used for CB-8 catalyst carrier (produced by Changling Catalyst Factory) and roasted at 900 ° C for 4 The carrier 5 (number Z ₅ ) is γ-alumina, which is obtained from spherical alumina (produced by Changling Catalyst Factory) used for the CB-8 catalyst carrier after calcination at 650°C for 4 hours. Carrier 6 (No. Z ₆ ) is γ-alumina, which is obtained by calcining spherical alumina (produced by Changling Catalyst Factory) at 650°C for 4 hours for CB-6 catalyst carrier. Carrier 7 (No. Z ₇ ) is γ _- alumina. The γ-alumina is obtained by calcining strip-shaped alumina (produced by Changling Catalyst Factory) at 650°C _for 4 hours. middle. Among them, the crystal phase is measured by X-ray diffraction method; the specific surface and pore volume are measured by low-temperature nitrogen adsorption BET method, and the amount of L acid is measured by infrared pyridine adsorption method, according to "Industrial Catalyst Analysis and Test Characterization", P353-360, Hydrocarbon Processing Press, determined by the method described in 1990.

Table 1 carrier number carrier type Specific surface, ^m2 /g Pore volume, ml/g crystal phase Acid content, A/g ^cm2 Z ₁ Z ₂ Z ₃ Z ₄ Z ₅ Z ₆ Z ₇ SiO ₂ SiO ₂ activated carbon Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ Al ₂ O ₃ 401672888124153190175 0.950.390.560.490.470.490.44 Amorphous Amorphous Amorphous δγγγ 1.70.4-4.813.117.313.4

(2) Preparation of catalyst

Weigh the above-mentioned carriers with different quantities and dry them at 100-150°C, respectively weigh the quantitative nickel acetate tetrahydrate to prepare nickel acetate solution and impregnate different carriers, and dry at 120°C to obtain nickel-containing carriers; respectively weigh quantitative KBH ₄ , and prepared into an aqueous solution, the KBH ₄ solution was added dropwise to the nickel-containing carrier at room temperature, the reaction proceeded immediately and hydrogen gas was released, after the drop, no hydrogen gas was released, indicating that the reaction had ended, and the obtained solid product was washed with distilled water Until there is no acid group, the numbers of the prepared catalysts are A～R, the amount of each substance used in the preparation process is listed in Table 2, and Table 3 provides the composition and physicochemical properties of catalysts A～R, wherein catalyst A has X-ray diffraction spectrum line shown in 1 in the middle, catalyst B has X-ray diffraction spectrum line shown in Figure 1 2, and catalyst C has X-ray diffraction spectrum line shown in Figure 1 3, catalyst D, G, H, I, J And L has X-ray diffraction line as shown in Figure 1 in 4, catalyst E and K have X-ray diffraction line as shown in Figure 1 5, catalyst F has X-ray diffraction line as shown in Figure 1 6, catalyst M and N has X-ray diffraction lines as shown in Figure 2, catalyst O has X-ray diffraction lines as shown in Figure 3, and catalysts P, Q and R have X-ray diffraction lines as shown in Figure 4.

Among them, the content of boron and nickel in the catalyst is dissolved by microwave digestion, and measured on the Janel-Ash1000 inductively coupled plasma direct reading spectrometer (ICP); The CuKα target is used on the instrument, the tube voltage is 40 volts, the tube current is 35 mA, the emission slit (D S) = 1°, the reception slit (R S) = 0.5 mm, and the anti-divergence slit (S S )=1° under the condition of measuring, Ni color filter; Catalyst specific surface and pore volume are to adopt low-temperature nitrogen adsorption method to measure on American Micromeristics ASAP2400 physical adsorption instrument.

Table 2 instance number carrier Nickel acetate solution KBH ₄ solution Feeding B/Ni atomic ratio type Dosage, grams Dosage of nickel acetate tetrahydrate, g Water consumption, ml KBH ₄ dosage, g Water consumption, ml 123456789101112131415161718 Z ₁ Z _{1 Z 1} Z ₁ Z ₁ Z ₁ Z ₁ Z ₁ Z ₁ Z 1 Z ₁ Z ₂ Z ₃ Z ₃ Z ₄ Z ₅ Z ₆ Z ₇ 5.05.05.05.05.05.05.05.05.05.05.05.05.05.05.05.05.05.0 4.03.02.01.00.50.21.01.01.01.01.01.01.00.951.01.01.01.0 9.09.09.09.09.09.09.09.09.09.09.06.08.05.05.05.05.05.0 2.161.621.080.540.270.110.650.540.430.330.220.540.540.520.540.540.540.54 12.012.012.012.012.012.012.012.012.012.012.08.010.07.07.07.07.07.0 2.52.52.52.52.52.53.02.52.01.51.02.52.52.52.52.52.52.5

table 3 instance number Catalyst number Ni, B content in the catalyst Specific surface m2/g Ni weight% B weight% Ni/B atomic ratio 123456789101112131415161718 ABCDEFGHIJKLMNOPQR 8.947.275.903.971.510.563.333.303.052.401.502.373.084.033.883.913.463.85 0.370.360.310.220.060.030.220.220.200.140.080.230.080.270.170.460.500.12 4.573.823.603.423.623.532.702.702.853.173.551.867.333.004.321.561.275.67 301321324341384395364365367374385451815131129177201194

It can be seen from Tables 1 to 3 that:

(1) In the process of preparing the catalyst, if the amount of reducing agent (BH ₄ ^- ) is small, that is, the ratio of B/Ni atoms fed is relatively small, the contents of Ni and B on the catalyst are relatively low, and most of the nickel ions are not reduced. As the amount of reducing agent increases, the content of Ni and B on the catalyst increases rapidly, but when the atomic ratio of B/Ni is greater than 2.5, the trend of increasing Ni content in the catalyst is not obvious; when the atomic ratio of B/Ni exceeds 2.0, The content of boron in the catalyzer is constant substantially, thereby although use lower or higher feed intake B/Ni atomic ratio also can prepare the Ni-B amorphous alloy catalyst provided by the invention, but feed intake B/Ni atomic ratio is little will make More Ni ions cannot be reduced, and the yield will be greatly reduced. When the B/Ni atomic ratio is too high, the cost of the catalyst will be increased. Therefore, it is more reasonable to control the B/Ni atomic ratio in the range of 1.5 to 3.0. (seeing examples 7-11).

(2) The difference of the support material has a great influence on the composition of the Ni-B amorphous alloy in the catalyst. Comparative examples 8, 12, 13, 15-18, it can be seen that under the same conditions of Ni and reducing agent dosage , the composition of Ni-B amorphous alloy in catalysts prepared on different types of supports is different, and the composition of Ni-B amorphous alloy in catalysts prepared by the same type of support is also different due to its different properties. The big difference, generally speaking, the support factors that affect the composition of the Ni-B amorphous alloy in the catalyst mainly include two aspects, one is the surface area and pore structure of the support, and the other is the chemical properties of the support, especially the acidity. The surface area and pore structure of the carrier will affect the mass transfer process of the reduction reaction, thus affecting the composition of the catalyst. Generally speaking, the greater the acid content of the carrier, the stronger the acid strength, and the greater the B content in the catalyst prepared under the same conditions, so for different The carrier material, the conditions for preparing Ni-B amorphous alloy catalyst should be different.

(3) The specific surface of the Ni-B amorphous alloy catalyst provided by the present invention depends on the specific surface of the carrier. By loading the amorphous alloy on a suitable carrier, the specific surface with desired value can be obtained, such as example 13 A Ni-B amorphous alloy catalyst with a specific surface as high as 815 m ² /g is prepared, but it is difficult to achieve such a high specific surface in the prior art.

Comparative example 1

Ni-P/SiO ₂ Amorphous Alloy Reference Catalyst

Ni-P/SiO ₂ Supported amorphous alloy catalyst S is provided by Deng Jingfa et al. Its preparation method is referred to Appl.catal.37,339～340,1988, and its composition is Ni11.70% by weight, P1.3% by weight, and the rest It is SiO ₂ , and its Ni and P contents are dissolved by microwave digestion method, and measured on Jannel-Ash-1000 inductively coupled plasma direct reading spectrometer (ICP).

Comparative example 2

Preparation of Large Surface Ni-La-P Amorphous Alloy Reference Catalyst.

According to the conditions described in example 6 in CN1073726A and the amount of each component, a large surface Ni-La-P amorphous alloy catalyst T is prepared, and its composition is Ni87.4 wt%, La0.4 wt%, P12.2 by ICP. % by weight, the specific surface measured by the same method as in Examples 1-18 is 91 ^m2 /g.

Comparative example 3

Preparation of Polycrystalline Nickel Reference Catalyst.

Weigh 5 grams of carrier Z ₁ , impregnate it with 9.82 grams of nickel nitrate solution with a concentration of 8.35% by weight, dry it at 100°C for 4 hours, bake it at 500°C for 3 hours, and then reduce it with hydrogen at 460°C for 4 hours to obtain ginseng. Bi reminder

Agent u, the catalyst contains Ni5% by weight, and the Ni content is also determined by the ICP method.

Instances 19-25

The following examples illustrate the thermal stability of the catalysts provided by this invention.

Weigh each 5 mg of catalysts B, C, D, E, L, M, and N, and measure them on the differential scanning analyzer (DSC) of Du Pont2100 thermal analysis system at a rate of temperature increase of 10°C/min under nitrogen atmosphere Its DSC curve and crystallization temperature, the DSC curves of catalysts B, C, D and E are shown in 7, 8, 9 and 10 in Fig. 5 respectively, and the highest crystallization temperature of each catalyst is shown in Table 4.

It can be seen from Fig. 5 that three phase transition peaks appear after the catalyst provided by the present invention is heated up, and the peak temperatures are respectively located around 175, 280 and 390°C. The enthalpy change value of the phase transition process represented by 280°C increases. In conjunction with the results in Table 4, it can be seen that the third crystallization peak temperature (i.e. the highest crystallization peak temperature) of the catalyst is related to the composition of the Ni-B amorphous alloy in the catalyst, and the higher the B content in the Ni-B amorphous alloy The higher its highest peak temperature, in addition, the thermal stability of the catalyst provided by the present invention is obviously higher than that of Ni-B ultrafine particle amorphous alloy, for example, the three crystallization peak temperatures of the catalyst provided by the present invention are respectively located at 175 , 280, and 362-445°C, while the three crystallization peak temperatures of Ni-B ultrafine particle amorphous alloys are only 144.1, 253.4, and 341.4°C, respectively (see J.catal.150,435,1994).

Table 4 instance number Catalyst number Catalyst Ni/B atomic ratio Maximum crystallization peak temperature ℃ 19202122232425 BCDELMN 3.823.603.423.621.867.333.00 394388408398445362391

The following examples and comparative examples illustrate the application of the catalyst provided by the invention in the hydrogenation reaction of various unsaturated functional group compounds and the activity of the catalyst, and the selected hydrogenation reaction is as follows:

(1) Selective hydrogenation reaction of trace acetylene in ethylene

The above seven reactions basically represent all types of hydrogenation reactions of compounds containing unsaturated functional groups.

Instances 26-28

The application of the catalyst provided by the invention in the selective hydrogenation reaction of trace acetylene in ethylene.

The hydrogenation reaction is carried out on a continuous micro-reactor. The inner diameter of the reactor is 3 mm, and the length is 2000 mm. The catalyst used is D, M, N, and the catalyst loading is 0.04 g. %, hydrogen 2.56 mol%, the reaction conditions are, reaction temperature 110 ℃, reaction pressure 10.0 MPa, gas volume space velocity 9000 hours ^-1 , the composition of gas before and after reaction all adopts gas chromatograph on-line analysis, hydrogenation reaction catalyst is N , D, and M, the change of the conversion rate of acetylene with time is shown in 11, 12 and 13 in Fig. 6, respectively.

Comparative Examples 4-6

The following comparative examples illustrate that the activity of the catalyst provided by the invention in the selective hydrogenation reaction of trace amounts of acetylene in ethylene is significantly higher than that of the existing catalysts.

The device used for the hydrogenation reaction, the raw materials and the reaction conditions are the same as examples 26-28, except that the catalysts used are respectively the reference catalysts S, T and U prepared in Comparative Examples 1, 2 and 3, and the acetylene conversion rate varies with time as shown in Figure 6 Shown in 14, 15, 16.

Example 29

The application of the catalyst provided by the invention in the reaction of hydrogenation of toluene to produce methylcyclohexane.

The hydrogenation reaction is carried out in a 100 ml batch reactor, 50 ml of 20% by weight toluene solution in cyclohexane and 0.2 g of catalyst D are added to the reactor, and 1.0 MPa of hydrogen is charged into the still, emptied, and repeatedly charged Hydrogen three times to replace the air in the kettle, then fill in 4.0 MPa hydrogen, heat up to 140 °C and react for 1 hour under the condition of stirring speed of 64 times/min, cool, take out the reacted mixture, and analyze it with gas chromatography , and the results are listed in Table 5.

Comparative Example 7

This comparative example illustrates the activity of the catalyst provided by the present invention in the reaction of hydrogenation of toluene to produce methylcyclohexane.

The reaction device, raw materials and reaction conditions are the same as in Example 29, except that the catalyst used is the large-surface Ni-La-P amorphous alloy catalyst T prepared in Comparative Example 2. The reaction results are listed in Table 5.

table 5 instance number catalyst Toluene conversion weight % 29 Comparative Example 7 DT 19.7420.01 Example 30

The application of the catalyst provided by the invention in the reaction of hydrogenation of styrene to ethylbenzene.

Carry out the hydrogenation reaction of styrene by the method described in example 29, styrene consumption 50 milliliters, catalyst D consumption 0.2 gram, reaction temperature 60 ℃, reaction times 0.5 hour, all the other are with example 29, and reaction result is listed in table 6.

Comparative Examples 8-9

The following comparative examples illustrate the activity of the catalyst provided by the present invention in the hydrogenation of styrene to ethylbenzene.

The reaction apparatus, raw materials and reaction conditions are the same as in Example 30, except that the catalysts used are reference catalysts T and U prepared in Comparative Examples 2 and 3, respectively, and the reaction results are listed in Table 6.

Table 6 instance number catalyst Styrene conversion weight % 30 vs. Example 8 vs. Example 9 DTU 16.5416.600.10

Example 31

The application of the catalyst provided by the invention in the hydrogenation reaction of adiponitrile to prepare hexamethylenediamine.

Carry out adiponitrile hydrogenation reaction according to the method described in example 29, reaction raw material is the ethanol solution of 50 milliliters 15% by weight of adiponitrile, catalyst D consumption 0.2 gram, reaction temperature 100 ℃, reaction time 1 hour, all the other operating conditions are the same as example 29. The reaction results are listed in Table 7.

Comparative Example 10

This comparative example illustrates the activity of the catalyst provided by the present invention in the hydrogenation of adiponitrile to hexamethylenediamine.

The reaction device, raw materials and reaction conditions are the same as in Example 31, except that the catalyst used is the reference catalyst T prepared in Comparative Example 2, and the reaction results are listed in Table 7.

Table 7 instance number catalyst Conversion rate of ethanedinitrile by weight % 31 vs. Example 10 DT 20.9125.95

As can be seen from the results of Tables 5 to 7, (1) the activity of the catalyst provided by the present invention in the above-mentioned hydrogenation reaction is all suitable with the large surface Ni-La-P amorphous alloy catalyst described in CN1073726A, but the present invention Ni-B amorphous alloy only accounts for 4.19 weight percent in the catalyzer that provides, nickel content only has 3.97 weight percent, and nickel content is as high as 87.4 weight percent in the large surface Ni-La-P amorphous alloy catalyst, this illustrates that the present invention provides In the catalyzer, the relative content of the active nickel that catalyzes the reaction is much higher than the Ni-La-P large-surface amorphous alloy catalyst, (2) the activity of the catalyzer provided by the invention in the hydrogenation reaction of styrene is traditional The activity of the polycrystalline nickel catalyst is more than 165 times, and the nickel content is also lower than that of the polycrystalline nickel catalyst. In summary, the catalyst provided by the present invention is a low-nickel high-efficiency catalyst, which has incomparable advantages in the prior art.

Example 32

The application of the catalyst provided by the invention in the reaction of producing aniline by hydrogenation of nitrobenzene.

Carry out hydrogenation reaction by the method described in example 29, reaction raw material is the isopropanol solution of 50 milliliters 20% by weight of nitrobenzene, catalyst D load 0.2 gram, reaction temperature 89 ℃, reaction time 1 hour, all the other operating conditions are the same as example 29. The reaction results are listed in Table 8.

Table 8 instance number catalyst Conversion rate of nitrobenzene, weight % 32 D. 1.97

Example 33

The application of the catalyst provided by the invention in the reaction of cyclohexanol hydrogenation from cyclohexanone.

Carry out hydrogenation reaction by the method described in example 29, reaction raw material is the cyclohexane solution of 50 milliliters 30% by weight cyclohexanone, catalyst D load 0.2 gram, reaction temperature 95 ℃, reaction time 1 hour, all the other operating conditions are the same as example 29. The reaction results are listed in Table 9.

Table 9 instance number catalyst Cyclohexanone conversion, weight % 33 D. 0.49

Example 34

The application of the catalyst provided by the invention in the hydrogenation reaction of phenylacetylene.

Carry out hydrogenation reaction by the method described in example 29, reaction raw material is the cyclohexane solution of 50 milliliters 15% by weight of phenylacetylene, catalyst D load 0.2 gram, reaction temperature 22 ℃, reaction time 0.5 hour, all the other operating conditions are the same as example 29 , The reaction results are listed in Table 10.

Table 10 instance number catalyst Phenylacetylene conversion weight % Styrene selectivity % by weight 34 D. 5.71 100

Claims (12)

1. A Ni-B amorphous alloy catalyst, characterized in that it is composed of Ni-B amorphous alloy accounting for 0.1-30.0% by weight, porous carrier material accounting for 70.0-99.9% by weight, wherein the atomic ratio of Ni and B is 0.5 ~10.0. 2. The catalyst according to claim 1, characterized in that its composition is that the Ni-B amorphous alloy accounts for 1.0-12.0% by weight, and the porous carrier material accounts for 88.0-99.0% by weight. 3. The catalyst according to claim 1 or 2, characterized in that the specific surface of the catalyst is 10-1000 ^m2 /g. 4. The catalyst according to claim 3, characterized in that the specific surface of the catalyst is 100-1000 ^m2 /g. 5. The catalyst according to claim 1 or 2, characterized in that the atomic ratio of Ni and B is 1.0-8.0. 6. The catalyst according to claim 1 or 2, characterized in that the porous carrier material is selected from one or more of porous inorganic oxides, activated carbon, zeolites, and molecular sieves. 7. The catalyst according to claim 4, characterized in that the porous carrier material refers to silicon oxide, activated carbon or aluminum oxide. 8. The preparation method of the catalyst according to claim 1, characterized in that it comprises the step of mixing a nickel-containing porous carrier material with a solution containing BH ₄ ^-ions at a molar concentration of 0.5 to 10.0 in a temperature range from higher than the freezing point of the solution to 100° C. 0.1-10.0 B is in contact with Ni feeding atomic ratio. 9. The method according to claim 8, characterized in that, the solution containing BH ₄ ^-ions refers to an aqueous solution or alcohol solution containing BH ₄ ^-ions , and the precursor of BH ₄ ^-ions is selected from KBH ₄ or NaBH ₄ or their mixture. 10. The method according to claim 8 or 9, characterized in that the atomic ratio of B to Ni is 1.5-3.0. 11. The method according to claim 8 or 9, characterized in that the contacting is slowly adding the solution containing BH ₄ ^- ions into the nickel-containing carrier material at room temperature to 50°C. 12. The catalyst of claim 1 is used for catalytic hydrogenation of compounds containing unsaturated functional groups.

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