CN1200955A - Catalyst containing Ni-P amorphous alloy, its preparation method and application - Google Patents

Abstract

A supported catalyst containing Ni-P amorphous alloy is composed of 0.15-30.00 wt% nickel, 0.03-10.00 wt% phosphorus, 0.01-3.50 wt% boron and 56.50-99.81 wt% porous carrier material, The nickel exists in the form of Ni-P or Ni-B amorphous alloy, the atomic ratio of Ni and P in the Ni-P alloy is 0.5-10.0, and the atomic ratio of Ni and B in the Ni-B alloy is 0.5-10.0 The catalyst is prepared by contacting a porous support material containing Ni-B amorphous alloy with a solution containing H ₂ PO ₂ ^- and Ni ²⁺ at a temperature higher than the freezing point of the solution. The catalyst has higher hydrogenation activity than existing catalysts.

Description

Catalyst containing Ni-P amorphous alloy, its preparation and application

The invention relates to an amorphous alloy catalyst, its preparation method and application, more specifically to a nickel-phosphorous amorphous alloy catalyst, its preparation method and application.

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

CN 1073726A 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 The amorphous 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 2.5M KBH ₄ aqueous solution was added dropwise to 0.1M nickel acetate ethanol solution at 25°C under stirring, and the precipitate was washed successively with 6 milliliters of 8M ammonia and a large amount of distilled water, An amorphous Ni-B ultrafine particle catalyst is obtained, and the specific surface of the catalyst can reach 29.7 ^m2 /g, but the thermal stability of the Ni-B ultrafine particle is relatively low. The article also reported that the aqueous solution containing nickel acetate, sodium acetate and sodium hypophosphite was heated under stirring at 90 ° C, and the pH value of the solution was adjusted to 11 with NaOH solution, and the precipitate was washed with ammonia water and a large amount of distilled water in turn. .0 mol% and P 13.0 mol% amorphous Ni-P ultrafine particle catalyst, although the highest crystallization peak temperature of this Ni-P catalyst can reach 394.4 ° C, but its specific surface is only 2.78 ^m2 /g .

According to Applied Catalysis 37, 339-343, 1988, the method of chemical plating is adopted, that is to say, trisodium citrate (Na ₃ C ₆ H ₅ O ₇ ), nickel sulfate (NiSO ₄ ), hypophosphite di Mix the solution of sodium hydrogen (NaH ₂ PO ₂ ) and sodium acetate (CH ₃ COONa) with the silica gel carrier, heat to 363K (about 90°C) under stirring, keep the pH value of the solution at 5, react for about 2 hours, and use distilled water Washing the product and drying overnight at 340K can prepare a Ni-P amorphous alloy catalyst deposited on SiO ₂ . This supported Ni-P amorphous alloy catalyst not only has a larger specific surface (85 m ² /gram), and has better thermal stability (the highest crystallization peak temperature is 352 ℃), is a kind of catalyst that has industrial application prospect very much, yet, this supported Ni-P amorphous state alloy catalyst exists The following defects: first, the catalyst is to stir and heat the silica carrier with a mixed solution containing sodium dihydrogen phosphite, nickel sulfate, sodium acetate and trisodium citrate, and the trisodium citrate and sodium acetate in the solution As a complexing agent of nickel ions, it plays the role of controlling the concentration of nickel ions in the solution. The pH value controls the reduction rate of nickel ions and the formation rate of Ni-P amorphous alloy, that is, the control of pH value and the effect of trisodium citrate and trisodium citrate. The presence of sodium acetate makes the formation of Ni-P amorphous alloy slower, which is beneficial to the deposition of Ni-P amorphous alloy on the _SiO2 carrier, but even so, because the reduction reaction of nickel ions is carried out in the solution, the formation Only a small part of the Ni-P amorphous alloy can be deposited on the silicon oxide carrier, and most of the Ni-P amorphous alloy is attached to the wall or deposited on the bottom of the container, so that the Ni loaded on the SiO ₂ carrier The yield of -P amorphous alloys is still low and inhomogeneous. In addition, since amorphous alloys such as Ni-B and Ni-P can be used as catalysts for the reduction of nickel ions by dihydrogen hypophosphite ions (H ₂ PO ₂ ^- ) (see J.Phys.Chem.Vol.97, No. 32, P850, 1993), and the amount of Ni-P amorphous alloy not deposited on the silicon oxide carrier is far greater than the amount of Ni-P amorphous alloy deposited on the SiO ₂ carrier, which is even larger The speed at which the nickel ion reduction reaction deposits on the wall or the bottom of the container makes the yield of the Ni-P amorphous alloy loaded on the _SiO2 support lower. Second, although the presence of trisodium citrate and sodium acetate complexing agent can control the reaction rate of nickel ions, which is beneficial to the deposition of Ni-P amorphous alloy on the _SiO2 carrier, due to the shielding of complexing agent The effect also reduces the reduction degree of nickel ions at the same time, so that some nickel ions in the solution cannot be reduced by H ₂ PO ₂ ^- ions, which not only causes waste of resources, but also increases the cost of the catalyst. Third, the catalytic activity of this catalyst is still low.

Since Ni-B and Ni-P amorphous alloys can be used as catalysts for H ₂ PO ₂ ^-reduction of nickel ions, for example, Ni-B or Ni-P amorphous alloys are uniformly dispersed in a carrier in advance to make H ₂ PO ₂ ^- The reaction of reducing nickel ions is always carried out under the catalysis of the catalyst, which can ensure that the generated Ni-P amorphous alloy is fully loaded and evenly dispersed on the carrier. However, there is no uniform dispersion on the carrier in the prior art. Ni-P amorphous alloy in. J.Phys.Chem.98, 8504～ ⁸⁵¹¹ , 1993 showed that the research results of the Ni-B amorphous alloy law prepared by chemical reduction method showed that the reaction of divalent metal ions and reducing agent BH ₄ in aqueous solution consists of the following three steps: A separate reaction consists of:

Because the speed of the above three reactions is very fast, it is difficult to ensure that the formed Ni-B amorphous alloy is loaded on the carrier if the carrier and the reaction solution are simply mixed together by the prior art (such as the method of electroless plating). , not to mention the uniform dispersion of Ni-B amorphous alloy on the carrier, so there is no Ni-B amorphous alloy uniformly dispersed in the carrier in the prior art, how to load the Ni-B amorphous alloy To the carrier has also become a technical problem in the art.

In order to solve the problem of loading technology and to improve the catalytic activity of the amorphous alloy catalyst, the applicant invented "a Ni-B amorphous alloy catalyst, its preparation method and application", and published on October 15, 1996 Japan filed a patent application with the Patent Office (Application No. 96120054.5). The composition of the catalyst provided by the invention is that the Ni-B amorphous alloy accounts for 0.1-30.0% by weight, and the porous carrier material accounts for 70.0-99.9% by weight, wherein the atomic ratio of Ni and B is 0.5-10.0; the porous carrier material refers to Non-oxidative porous carrier materials, preferably one or more of porous inorganic oxides, activated carbon, zeolite, and molecular sieves. The porous inorganic oxides refer to Group IIA, Group IVB, Group IIIA, Oxides of Group IVA elements, preferably one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, and calcium oxide; Atomic molecular sieves, such as A-type zeolite, X-type zeolite, Y-type zeolite, ZSM series zeolite, mordenite, Beta zeolite, omega zeolite, phosphorus aluminum molecular sieve, titanium silicon molecular sieve, etc. The preferred porous carrier material is silicon oxide, aluminum oxide or Activated carbon. The preparation method of the catalyst comprises mixing a nickel-containing porous carrier material with a solution containing BH ₄ ^-ions at a molar concentration of 0.5-10.0 in a temperature range from higher than the freezing point of the solution to 100° C. Feed ratio contact. The invention successfully solves the technical problem of supporting Ni-B amorphous alloy, and prepares a novel supported Ni-B amorphous alloy catalyst. The preparation method of the catalyst abandons the traditional method of reducing nickel with NH ₄ ^- in the solution, and first impregnates the nickel onto the porous support material, and then reduces the nickel evenly distributed in the porous support material with the BH ₄ ^- solution , the generated Ni-B amorphous alloy can not only be loaded in the porous carrier material, but also the alloy can be more uniformly dispersed in the carrier. The activity of the Ni-B amorphous alloy catalyst prepared by this method is equivalent to that of the existing Ni-La-P large-surface amorphous alloy with the highest activity. However, in the prior art, there has not been a catalyst containing Ni-P amorphous alloy more uniformly dispersed in the carrier. The catalytic activity of existing Ni-P-containing amorphous alloy catalysts is also lower than that of Ni-La-P large-surface amorphous alloy catalysts.

The purpose of the present invention is to overcome the low shortcoming of existing Ni-P amorphous alloy catalyst catalytic activity, provide a kind of active higher load-type catalyst containing Ni-P amorphous alloy; Another object of the present invention It is to provide a preparation method of the catalyst with high yield of Ni and Ni-P amorphous alloy loaded on the carrier. The third purpose of the present invention is to provide the application of the catalyst.

The catalyst provided by the invention is composed of 0.15-30.00% by weight of nickel, 0.03-10.00% by weight of phosphorus, 0.01-3.50% by weight of boron and 56.50-99.81% by weight of porous carrier material. The nickel is made of Ni-P or Ni - B exists in the form of amorphous alloy and is loaded in the porous carrier material, the atomic ratio of Ni and P in the Ni-P alloy is 0.5-10.0, and the atomic ratio of Ni and B in the Ni-B alloy is 0.5-10.0.

The preparation method of the catalyst provided by the invention comprises mixing a porous carrier material containing Ni-B amorphous alloy with a mixture containing H ₂ PO ₂ ^- and Ni ²⁺ at a temperature higher than the freezing point of the solution to 100°C Solution contact reaction; the weight ratio of the porous carrier material containing Ni-B amorphous alloy to the Ni ²⁺ in the solution is 1000-1; the porous carrier material containing Ni-B amorphous alloy contains Ni-B The amorphous alloy is 0.10-20.00% by weight, and the atomic ratio of Ni to B is 0.5-10.0. The preparation method includes mixing a porous carrier material containing 0.10-20.00% by weight of Ni with a temperature higher than the freezing point of the solution to 100°C. A solution containing BH ₄ ^- ions with a molar concentration of 0.5-10.0 is subjected to a contact reaction at a boron-nickel feeding atomic ratio of 0.1-10.0; the molar concentration of H ₂ PO ₂ ^- in the mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ 0.01-5.00, the molar concentration of Ni ²⁺ is 0.01-5.00, and the atomic ratio of P and Ni in the solution is above 0.5.

The application of the catalyst provided by the 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 present invention, its preferred composition is 0.50-10.00 wt% of nickel, 0.20-5.00 wt% of phosphorus, 0.02-2.00 wt% of boron, and 83.00-99.38 wt% of porous carrier material; a more preferred composition is: nickel 0.50-6.00% by weight, phosphorus 0.10-2.50% by weight, boron 0.02-1.00% by weight, porous carrier material 90.50-99.38% by weight.

The atomic ratio of Ni and P in the catalyst Ni-P amorphous alloy is preferably 1.0-5.0, and the atomic ratio of Ni and B in the Ni-B amorphous alloy is preferably 0.5-5.0.

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, IIIA, and IVA elements, preferably one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide, and calcium oxide; the zeolite, Molecular sieve refers 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 sieve, etc.; preferred The preferred porous carrier material is 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 present invention, the active component nickel can all exist in an amorphous state, and at this moment, on the X-ray diffraction spectrum figure measured by the CuKα target, there is a wider diffuse scattering peak at 2θ=45°C (as shown in Figure 1, 1 shown); in some cases, the peak shape of the diffusion peak is changed due to different carriers, such as when activated carbon is used as the carrier, the peak shape of the diffusion peak is sharper (as shown in 2 in Figure 1) , in other cases, the diffusion peak may be covered by the diffraction peak of the carrier at the same position (as shown in 2 and 3 in Figure 1).

According to the catalyzer provided by the present invention, its DSC curve is different depending on the carrier, can have a phase transition peak temperature (as shown in Figure 3～4) and can also have more than one phase transition peak temperature (as shown in Figure 2 ).

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

1. Prepare the porous carrier material containing Ni-B amorphous alloy according to the method described in CN96120054.5, that is, at a temperature higher than the freezing point of the solution to 100°C, the porous carrier containing 0.10 to 20.00% by weight of nickel and the molar concentration A solution containing BH ₄ ^-ions of 0.5 to 10.0 is subjected to contact reaction at an atomic ratio of boron to nickel of 0.10 to 10.00, and the solid product is washed with distilled water until there are no acid radicals to obtain a porous carrier material containing Ni-B amorphous alloy, which contains Ni - B amorphous alloy 0.10-20.00% by weight, the atomic ratio of Ni to B is 0.5-10.00;

2. At a temperature higher than the freezing point of the solution to 100 ° C, the porous carrier material containing Ni-B amorphous alloy is contacted with a mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ ; the H in the mixed solution The molar concentration of ₂ PO ₂ ^- is 0.01-5.00, the molar concentration of Ni ²⁺ is 0.01-5.00, the atomic ratio of P and NI is more than 0.50, and the solid product is washed until there are no acid radicals to obtain the catalyst provided by the invention.

The nickel-containing porous carrier material described in 1 can be commercially available nickel-containing porous carrier material, and nickel can also be introduced into the carrier by conventional methods, such as can be prepared by impregnating the porous carrier material with a soluble nickel salt solution, and the impregnation can also It can be replaced by other methods such as kneading method. When the porous carrier material is zeolite or molecular sieve or other exchangeable carrier materials, the introduction of nickel can also adopt ion exchange method. The soluble nickel salt can be selected from nickel chloride, nickel sulfate 1. One or more of soluble nickel carboxylates, preferably nickel chloride or nickel acetate, and the nickel content in the nickel-containing porous carrier material is preferably 0.8-8.0% by weight.

The nickel-containing porous carrier material described in 1 is preferably pre-dried at 90-200°C for more than 3 hours.

The BH ₄ ^-containing solution described in 1 may be a BH ₄ ^-containing aqueous solution or an alcohol solution, and the precursor of the BH ₄ ^- ion is selected from KBH ₄ or NaBH ₄ or a mixture thereof.

Although the temperature of the contact reaction between the nickel-containing porous carrier material and the BH ₄ ^-ion solution as described in 1 can be carried out at a temperature higher than 100°C, in order to save energy, the reaction is generally controlled within the range of higher than the freezing point of the solution to 100°C, preferably Control at room temperature to 50°C; the time of contact reaction depends on the reaction temperature. When the reaction temperature is higher, the reaction speed is faster and the reaction time can be shorter. When the reaction temperature is lower, the reaction speed is slower and the reaction time can be shorter. Long, because a large amount of hydrogen gas will be released during the reaction, so when no hydrogen gas is released, it indicates that the reaction has ended. The time of contact reaction refers to the time from the beginning of the reaction to the time when no hydrogen gas is released.

The contact reaction between the nickel-containing porous carrier material and the BH ₄ ^-ion solution described in 1 can be mixed directly, or the solution containing BH ₄ ^-ion can be slowly added dropwise to the carrier material, preferably slowly dropwise The way.

The content of the Ni-B amorphous alloy in the porous carrier material containing the Ni-B amorphous alloy described in 2 is preferably 0.5-8.0% by weight, and the atomic ratio of Ni to B is preferably 1.0-5.0.

The mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ ions mentioned in 2 is preferably an aqueous solution containing H ₂ PO ₂ ^- and Ni ²⁺ , and the precursor of the H ₂ PO ₂ ^- can be optional with or without crystallization KH ₂ PO ₂ or NaH ₂ PO ₂ or mixtures thereof; the precursor of Ni ²⁺ is selected from soluble nickel salts, such as one or more of nickel chloride, nickel sulfate, and soluble nickel carboxylate, preferably Nickel chloride or nickel acetate; the atomic ratio of P and Ni in the solution is preferably more than 1.0, preferably 4.0-7.0.

The weight ratio of the porous carrier material containing Ni-B amorphous alloy described in 2 to Ni ²⁺ in the solution may be 1000-1, preferably 5-200, more preferably 5-100.

In 2, the contact reaction temperature of the porous carrier material containing Ni-B amorphous alloy with the mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ can be higher than 100°C, but in order to save energy, the reaction temperature Generally, it is controlled at a temperature higher than the freezing point of the solution to 100°C, preferably room temperature to 50°C; the contact reaction time depends on the reaction temperature. When the reaction temperature is higher, the reaction speed is faster, the reaction time can be shorter, and the reaction temperature is lower. When the reaction speed is slow, the reaction time can be longer, because H ₂ PO ₂ will release hydrogen when reducing nickel ions, and when no hydrogen is released, it indicates that the reaction has ended. The time of contact reaction refers to the time from the beginning of the reaction to no hydrogen release time.

As described in 2, the porous carrier material containing Ni-B amorphous alloy is contacted with the mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ , the two can be directly mixed and allowed to stand for contact reaction, or they can be mixed Afterwards, the contact reaction is carried out under stirring, and the mixed solution containing H ₂ PO ₂ ^- and Ni ²⁺ can also be slowly added dropwise to the porous carrier material containing Ni-B amorphous alloy, preferably directly mixed and then stirred The method of carrying out the contact reaction.

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. Catalyst activity is high, and the catalyst provided by the invention has higher catalytic activity than prior art, for example, with 3.98% by weight nickel provided by the invention, on SiO ₂ on loading Ni-P and Ni-B amorphous State alloy catalyst, Ni-La-P large surface amorphous alloy catalyst disclosed by CN 1073726A, AppliedCatalysis 37,339～343, 1988 disclosed nickel-containing 11.70% by weight loaded Ni-P/SiO ₂ catalyst, and containing The traditional polycrystalline nickel catalyst of 5.0% by weight of nickel is used for the selective hydrogenation reaction of trace acetylene in ethylene under the conditions of reaction temperature 110°C, reaction pressure 10.0 MPa and gas volume space velocity 9000 hours ^-1 , and acetylene The conversion rates are shown as 4, 7, 8, and 9 in Fig. 6, which shows that the activity of the catalyst provided by the present invention is much higher than that of other catalysts, even much higher than that of the large-surface amorphous with the highest hydrogenation activity in the prior art. state alloy catalyst, and the Ni content of the above-mentioned catalyst provided by the invention is far lower than the Ni-La-P large surface amorphous alloy catalyst (Ni content 87.4% by weight), which further illustrates that the catalyst provided by the invention is a low Nickel efficient catalyst.

2. The specific surface of the catalyst can be adjusted arbitrarily. Because the specific surface of the catalyst provided by the present invention changes with different supports, different supports can be used to adjust the specific surface of the catalyst. The specific surface can be 10 to 1000 m ^/ gram, or even 100～1000 ^m2 /g, and the specific surface of ultrafine particle Ni-B and Ni-P amorphous alloy catalyst disclosed in Journal of Catalysis 150, 434～438, 1994 can only reach 29.7 ^m2 /g and 2.78 m ² /gram, the specific surface of Ni-P/SiO ₂ disclosed in Applied Catalysis 37,339～343,1988 is only 85 ^m2 /gram, and the Ni-RE-P large-surface amorphous alloy with the largest specific surface is also only It can reach 130 ^m2 /g.

3. The thermal stability of the catalyst is relatively high. The catalyst provided by the present invention has a relatively high thermal stability, and its highest crystallization peak can reach 434° C. ₂ The highest crystallization peak temperature of the catalyst is only 353°C, and the highest crystallization peak temperature of the Ni-La-P large-surface amorphous alloy catalyst is only 278°C.

The preparation method of the catalyst provided by the invention is to first make the Ni-B amorphous alloy loaded on the porous carrier, and then mix the carrier material containing the Ni-B amorphous alloy with the dihydrogen phosphite (H ₂ PO ₂ ^- ) and a mixed solution of nickel ions (Ni ²⁺ ), since the Ni-B amorphous alloy can be used as a catalyst ^for H ₂ PO ₂ -reduction of Ni ²⁺ , H ₂ PO ₂ ^- The reaction of reducing Ni ²⁺ to generate Ni-P amorphous alloy is carried out in the carrier, so as to ensure that the Ni-P amorphous alloy generated at the beginning can be fully loaded on the surface or in the pores of the porous carrier material. As the reaction proceeds, the generated Ni-P amorphous alloy becomes a catalyst for the above-mentioned reduction reaction, so the subsequent reduction reaction is only carried out in the carrier, so the Ni-P amorphous alloy generated later can also be fully loaded on the carrier. On the porous carrier material, the result is that all the Ni-P amorphous alloys generated are all loaded in the porous carrier material, and according to the Ni-P/ _SiO2 catalyst preparation method disclosed in AppliedCatalysis 37,339～343,1988, generate Only 20.1% by weight of the Ni-P amorphous alloy was loaded on the carrier, and the others were attached to the wall or scattered on the bottom of the container. In addition, the preparation method of the catalyst provided by the present invention does not use complexing agents such as trisodium citrate, and the nickel ions in the solution are easily reduced by H ₂ PO ₂ ^- , so the yield of nickel is greatly improved. For example, the method provided by the present invention is used to prepare The nickel yield can reach 21.3-98.4% by weight when the catalyst is used. When the atomic ratio of P and Ni is controlled above 4, the nickel yield can be guaranteed to reach more than 50% by weight, and even up to 98.4% by weight. Applied Catalysis37, 339-343 , The method disclosed in 1988, the nickel yield is only 16.9% by weight.

Fig. 1 is the X-ray diffraction spectrogram of the catalyst containing Ni-P amorphous alloy of different supports provided by the present invention;

Fig. 2 is provided by the invention with SiO ₂ is the DSC curve of the catalyst containing Ni-P amorphous alloy of carrier;

Fig. 3 is the DSC curve of the catalyst containing Ni-P amorphous alloy with activated carbon as the carrier provided by the invention;

Fig. 4 is the DSC curve of the catalyst of the Ni-P amorphous alloy with δ-alumina as the carrier provided by the present invention;

Fig. 5 is the DSC curve of the Ni-La-P large surface amorphous alloy catalyst disclosed by CN 1073726A;

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 in any form.

Instances 1 to 15

(1) Porous carrier material

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-Al ₂ O ₃ , and this δ-Al ₂ O ₃ is spherical alumina (produced by Changling Catalyst Factory) used for CB-8 catalyst carrier Calcined at 900°C for 4 hours, Z ₁ to Z ₄ are all 80 to 120 mesh particles. The physical and chemical properties of the above carriers Z ₁ -Z ₄ are listed in Table 1. The crystal phase is determined by X-ray diffraction method; the specific surface area and pore volume are determined by low-temperature nitrogen adsorption BET method.

Table 1 carrier number carrier type Specific surface, ^m2 /g Pore volume, ml/g crystal phase Z ₁ SiO ₂ 401 0.95 amorphous Z ₂ SiO ₂ 672 0.39 amorphous Z ₃ activated carbon 888 0.56 amorphous Z ₄ Al ₂ O ₃ 124 0.49 δ

(2) Preparation of porous carrier material containing Ni-B amorphous alloy

Weigh quantitative carriers Z ₁ ~ Z ₄ respectively, and dry them at 100-150°C, respectively weigh quantitative nickel acetate tetrahydrate and distilled water to prepare nickel acetate aqueous solution and impregnate different carriers, and dry at 120°C to obtain nickel-containing carriers. Weigh quantitative KBH ₄ respectively and make an aqueous solution. Add the KBH ₄ aqueous solution dropwise to the nickel-containing carrier at room temperature. The reaction proceeds immediately and releases hydrogen. The obtained solid product was washed until there were no acid radicals, and the porous carrier materials S ₁ ~ S ₆ containing Ni-B amorphous alloy were prepared. Table 2 shows the amount of each material used in the preparation process, and Table 3 shows the obtained Ni-B-containing amorphous alloy. -The content of Ni-B amorphous alloy in the porous carrier material of B amorphous alloy, the specific surface area of S ₁ ~ S ₆ , among which the content of boron and nickel was dissolved by microwave digestion method, and the Jarrel-Ash 1000 inductively coupled Measured on the plasma direct reading spectrometer (ICP), the specific surface and pore volume determination methods are the same as before.

Table 2 carrier Nickel acetate solution KBH ₄ solution The number of the obtained Ni-B-containing carrier type Dosage, grams Dosage of nickel acetate tetrahydrate, g Water consumption, grams KBH ₄ dosage, g Water consumption, grams Z ₁ Z ₁ Z ₂ Z ₃ Z ₄ Z ₄ 5.05.05.05.05.05.0 0.20.50.20.50.21.0 9.09.09.09.09.05.0 0.110.270.110.270.110.54 12.012.012.012.012.07.0 S ₁ S ₂ S ₃ S ₄ S ₅ S ₆

table 3 Carrier No. containing Ni-B Ni-B content, wt% Ni to B atomic ratio Specific surface, ^m2 /g S ₁ 0.59 3.44 396 S ₂ 1.57 4.63 385 S ₃ 0.55 1.84 652 S ₄ 1.56 3.41 868 S ₅ 0.65 3.81 125 S ₆ 3.96 1.27 129

(3) Preparation of catalyst

Weigh quantitative Ni-B-containing amorphous alloy carriers S ₁ ~ S ₆ respectively, weigh quantitative nickel acetate tetrahydrate and sodium dihydrogen phosphite monohydrate and dissolve in quantitative distilled water to form a mixed solution, and The weighed carriers S ₁ ~ S ₆ containing Ni-B amorphous alloy were added to the prepared mixed solution at different temperatures, stirred, and the reaction was carried out on the carrier immediately, and hydrogen gas was released. After reacting for different times, When no hydrogen gas is released, it indicates that the reaction has ended, and the solid product obtained by washing with distilled water is free of acid radicals to obtain the catalyst provided by the present invention, which is numbered A～O, and the amount of each substance and the reaction conditions in the preparation process are listed in Table 4 Among them, Table 5 shows the yield and nickel yield of the Ni-P amorphous alloy loaded on the carrier, and Table 6 shows the composition and physicochemical properties of catalysts A~O. Wherein catalysts A～L have X-ray diffraction lines as shown in Figure 1 1, catalyst M has X-ray diffraction lines as shown in Figure 1 2, and catalysts N and O have X-ray diffraction lines as shown in Figure 1 3 spectral line.

The yield of the Ni-P amorphous alloy loaded on the carrier refers to that the amount of the Ni-P amorphous alloy loaded on the carrier accounts for the Ni-P amorphous alloy total amount generated (including not loaded to the carrier The weight percentage of the Ni-P amorphous alloy on the surface), because the carrier used is 80-120 mesh particles, and the generated non-supported Ni-P amorphous alloy is a very fine (greater than 200 mesh) powder, Therefore, sieve out particles above and below 120 mesh, measure the content of Ni-P amorphous alloy respectively, and then calculate the yield according to the following formula:

The yield of the Ni-P amorphous alloy loaded on the carrier =

The nickel yield=(the total amount of Ni in the solid product-the amount of Ni in the original carrier)/drop into the total amount of Ni in the solution×100%

The content of boron, nickel and phosphorus was measured on a Jarrel-Ash 1000 inductively coupled plasma direct reading spectrometer (ICP) by microwave digestion; Use CuKα target, tube voltage 40KV, tube current 35mA, emission slit (D S) = 1°, acceptance slit (R S) = 0.5mm, anti-divergence slit (S S) = 1° Determination of conditions, Ni filter; catalyst specific surface determination method is the same as before.

Table 4 instance number Ni-B containing amorphous alloy carrier Concentration of mixed solution, mol/L Amount of mixed solution, ml P to Ni atomic ratio Reaction temperature, °C reaction time, time type Dosage, grams Ni ²⁺ H ₂ PO ₂ ^- 1 S ₁ 5.00 0.10 0.10 40.00 1.00 25 3 2 S ₁ 5.00 0.10 0.20 40.00 2.00 25 3 3 S ₁ 5.00 0.10 0.30 40.00 3.00 25 3 4 S ₁ 5.00 0.10 0.40 40.00 4.00 25 3 5 S ₁ 5.00 0.10 0.50 40.00 5.00 25 3 6 S ₁ 5.00 0.10 0.60 40.00 6.00 25 3 7 S ₁ 5.00 0.10 0.70 40.00 7.00 25 3 8 S ₂ 5.00 0.05 0.25 40.00 5.00 8 10 9 S ₂ 5.00 0.05 0.30 40.00 6.00 25 2 10 S ₂ 5.00 0.05 0.35 40.00 7.00 50 1.5 11 S ₂ 5.00 0.05 0.40 40.00 8.00 90 1 12 S ₃ 5.00 0.10 0.40 40.00 4.00 25 3 13 S ₄ 5.00 0.12 0.48 40.00 4.00 25 2 14 S ₅ 5.00 0.14 0.56 40.00 4.00 25 3 15 S ₆ 5.00 0.22 0.88 40.00 4.00 25 1.5

table 5 instance number Yield of Ni-P amorphous alloy loaded on the carrier, weight % Nickel yield, weight % 1 100 21.3 2 100 36.2 3 100 56.2 4 100 76.0 5 100 75.8 6 100 81.4 7 100 86.7 8 100 51.2 9 100 66.0 10 100 67.7 11 100 73.9 12 100 50.0 13 100 93.6 14 100 90.9 15 100 98.4

Table 6 instance number Catalyst number Catalyst composition, weight % Specific surface ^m2 /g Ni Ni in the form of Ni-P P B Ni/P atomic ratio in Ni-P alloy 1 A 1.55 0.99 0.11 0.03 4.75 384 2 B 2.23 1.67 0.27 0.03 3.26 374 3 C 3.12 2.56 0.46 0.03 2.94 364 4 D. 3.99 3.43 0.52 0.03 3.48 341 5 E. 3.98 3.42 0.52 0.03 3.47 341 6 f 4.22 3.66 0.55 0.03 3.51 338 7 G 4.45 3.89 0.62 0.03 3.31 330 8 h 2.71 1.20 0.27 0.06 2.34 366 9 I 3.03 1.52 0.33 0.06 2.43 367 10 J 3.07 1.56 0.36 0.06 2.29 366 11 K 3.21 1.70 0.37 0.06 2.42 365 12 L 2.79 2.29 0.27 0.05 4.47 446 13 m 6.46 4.98 0.63 0.08 4.17 786 14 N 6.16 5.54 1.79 0.03 1.63 135 15 o 12.96 9.50 2.71 0.50 1.84 136

Comparative example 1

Preparation of Ni-P/ _SiO2 Amorphous Alloy Reference Catalyst.

According to the method described in Applied Catalysis 37, 339-340, 1988, in the presence of sodium citrate (Na ₃ C ₆ H ₅ O ₇ H ₂ O) 10 g/L, NiSO ₄ 6H ₂ O 20 g/L, CH ₃ COONa 10 g/L and NaH ₂ PO ₂ 2H ₂ O 10 g/L mixed solution 40 ml, add 5 g Z ₁ carrier, stir and heat the mixed solution to 363K, keep constant temperature for 2 hours, wash the solid product with distilled water To no acid radicals, dry at 340K overnight to obtain Ni-P/SiO ₂ amorphous alloy catalyst, its code is P. The catalyst contains 0.6% by weight of Ni and 0.07% by weight of P, wherein the yield of Ni-P amorphous alloy loaded on _SiO2 is 20.1% by weight, and the yield of nickel is 16.9% by weight.

As can be seen from the results of Tables 4 to 6 and Comparative Example 1:

(1) prepare catalyzer by the method provided by the invention, the whole load of the Ni-P amorphous alloy of generation is in the porous support material, does not have non-loaded Ni-P amorphous alloy to generate, and press AppliedCatalysis 37,339～ 340, when the method described in 1988 prepared Ni-P/SiO ₂ amorphous alloy catalysts, most of the Ni-P amorphous alloy generated was not loaded on SiO ₂ carriers, and the Ni-P amorphous alloys loaded on SiO ₂ The yield of the crystalline alloy is only 20.1% by weight, which shows that the method provided by the invention is superior to the prior art.

(2) when preparing catalyzer by the method provided by the invention, nickel yield can reach 21.3～98.4%, obviously higher than Applied Catalysis 37,339～340, the nickel yield (16.9 weight %) that the method disclosed in 1988 obtains, also It shows that the method provided by the invention is better than the prior art. In addition, the amount of H ₂ PO ₂ ^- when preparing the catalyst according to the method provided by the present invention has a great influence _on the reduction degree of Ni ²⁺ . When the amount of H ₂ PO ₂ ^- is small, the nickel yield is _low. ^- When the amount of H 2 PO 2 - increases, the nickel yield increases, but when the atomic ratio of P to Ni in the solution is greater than 4, the trend of nickel yield increasing with the increase of H ₂ PO ₂ ^- amount slows down, which shows that when P and Ni in the solution The catalyst provided by the invention can be obtained when the atomic ratio of Ni is greater than 0.5, and when the atomic ratio of P and Ni is less than 4.0, the nickel yield is low, and when it is greater than 7.0, the nickel yield cannot be obtained while the raw material is wasted. Therefore, it is more reasonable to control the atomic ratio of P and Ni in the solution at 4-7. At this time, under other suitable conditions, a nickel yield greater than 50% by weight can be obtained, and even a nickel yield of 98.4% by weight can be achieved. Rate.

(3) when preparing catalyzer according to the method provided by the invention, temperature of reaction and reaction time can change in a large range, and the higher required reaction time of temperature of reaction is less, but too high energy of meeting consumption of reaction temperature, reaction The temperature is too low, and the required reaction time is too long. Therefore, although the reaction temperature can be carried out at a temperature above the freezing point of the solution and at a temperature higher than 100° C., in order to take into account both the reaction time and energy consumption, the reaction temperature is preferably room temperature to 50 °C. ℃.

(4) Because the Ni-B amorphous alloy acts as a catalyst for the reaction of H ₂ PO ₂ ^-reduction of Ni ²⁺ , the content of the Ni-B amorphous alloy in the carrier has a great influence on the reaction rate. The higher the content of Ni-B amorphous alloy, the faster the reaction, so the reaction temperature and reaction time should be different with different Ni-B amorphous alloy content in the carrier.

Comparative example 2

The Ni-P/SiO ₂ amorphous alloy catalyst Q was provided by Deng Jingfa. For its preparation method, see Applied Catalysis 37, 339-340, 1988. The catalyst contained 11.70% by weight of Ni, 1.30% by weight of P, and the rest was SiO ₂ . Catalyst Q has a specific surface area of 85 ^m2 /g.

Comparative example 3

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

Prepare large surface Ni-La-P amorphous alloy catalyst R by the conditions described in example 6 and the amount of each component in CN 1073726A, its composition is Ni 87.4%, La 0.4 weight%, P 12.2 weight%, its specific surface It is 91 m ² /g.

Comparative example 4

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. Compared with catalyst S, ICP analysis results showed that the catalyst contained 5.0% by weight of Ni.

Instances 16-18

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

Take by weighing each 5 milligrams of catalyst E, M, and N, and measure its DSC curve and crystallization temperature on the differential scanning analyzer (DSC) of DuPont 2100 thermal analysis system with a rate of rise of 10 ° C/min under a nitrogen atmosphere. The DSC curves are shown in Figures 2 to 4 in turn.

Comparative example 5

Take by weighing 5 milligrams of catalyst R, measure its DSC curve by the conditions described in example 16～18, the result is as shown in Figure 5.

Above-mentioned result surface the thermal stability of _the catalyzer that the present invention provides is not lower than existing Ni-P/SiO ₂ amorphous alloy catalysts (Ni-P/SiO The highest crystallization peak temperature is 353 ℃, and the present invention provides The highest crystallization peak temperature of the catalyst is higher than 350°C, and the highest crystallization peak temperature of the catalyst based on silicon oxide can reach 434°C), which is significantly higher than that of the most active Ni-La-P large-surface amorphous thermal stability of alloy catalysts. The above results also show that the catalyst provided by the present invention depends on the difference of the carrier material, and its crystallization process can be a phase change process, and it can also be more than one phase change process. When it is shown on the DSC curve, one or More than one phase transition peak.

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 19-21

The following examples illustrate the application of the catalyst provided by the invention in the selective hydrogenation reaction of trace acetylene in ethylene and the catalytic activity of the catalyst in this reaction.

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 catalysts used are E, M, O, and the catalyst loading is 0.04 grams. %, hydrogen 2.56 mol%, the reaction conditions are, reaction temperature 110 ℃, reaction pressure 1.0 MPa, gas volume space velocity 9000 hours ^-1 , the composition of gas before and after reaction all adopts gas chromatograph on-line analysis, catalyst is E, O, At M, the curves of the conversion of acetylene with time are shown as 4, 5 and 6 in Fig. 6 in turn.

Comparative Examples 6-8

The following comparative examples illustrate that the catalytic activity of the catalyst provided by the present invention is obviously higher than that of the existing catalyst.

The device used for hydrogenation reaction, raw materials and catalyst loading and reaction conditions are the same as examples 19-21, except that the catalyst used is different. The catalyst is R, Q, S in turn, and the change curve of acetylene conversion rate with time is successively 7 and 8 in Fig. 6 , and 9.

The results in Figure 6 show that the catalytic activity of the catalyst provided by the present invention is not only much higher than the traditional polycrystalline nickel catalyst, but also significantly higher than the Ni-P/SiO ₂ supported catalyst and the highest catalytic activity in the prior art Ni- La-P large-surface amorphous alloy catalyst, while the nickel content in the catalyst provided by the invention is far lower than Ni-La-P large-surface amorphous alloy catalyst, which shows that the catalyst provided by the invention is a low-nickel catalyst , High-efficiency catalyst, has the incomparable superiority of the existing technology.

Example 22

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

The hydrogenation reaction is carried out in a 100 ml batch reactor, 50 ml of 20% by weight toluene in cyclohexane and 0.2 gram of catalyst E are added to the reactor, the reactor is filled with 4.0 MPa hydrogen, and the temperature is raised to 140 °C, reacted for 1 hour at a stirring speed of 64 times/min, took out the reacted mixture after cooling, and analyzed it by gas chromatography. The results are listed in Table 5.

table 5 instance number catalyst Toluene conversion, wt% twenty two E. 2.46

Instances 23-24

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

Carry out styrene hydrogenation reaction by the method for example 22, styrene consumption 50 milliliters, reaction temperature is respectively 60 ℃ and 130 ℃, reaction time 0.5 hour, all the other operating conditions are the same as example 22, and the results are listed in table 6.

Table 6 instance number Reaction temperature, °C catalyst Styrene conversion, weight % 2324 60130 EE 0.2291.01

Example 25

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

Carry out adiponitrile hydrogenation reaction by the method for example 22, reaction raw material is the ethanol solution of 50 milliliters 15% by weight of adiponitrile, reaction temperature 100 ℃, reaction time 1 hour, all the other operating conditions are the same as example 22, reaction result is listed in the table 7 in.

Table 7 instance number catalyst Conversion rate of adiponitrile, weight % 25 E. 1.49

Example 26

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

Carry out nitrobenzene hydrogenation reaction by the method for example 22, reaction raw material is the isopropanol solution of 50 milliliters of 20% by weight nitrobenzene, reaction temperature 89 ℃, reaction time 1 hour, all the other operating conditions are the same as example 22, the results are listed in Table 8.

Table 8 instance number catalyst Conversion rate of nitrobenzene, weight % 26 E. 1.41

Example 27

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

Carry out cyclohexanone hydrogenation reaction by the method for example 22, reaction raw material is the cyclohexane solution of 50 milliliters 30% by weight cyclohexanone, reaction temperature 95 ℃, reaction time 1 hour, all the other operating conditions are the same as example 22, and the results are listed in Table 9.

Table 9 instance number catalyst Cyclohexanone conversion, weight % 27 E. 0.46

Example 28

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

Carry out phenylacetylene hydrogenation reaction by the method for example 22, reaction raw material is the cyclohexane solution of 50 milliliters 15% by weight of phenylacetylene, catalyst agent E consumption 0.2 gram, reaction temperature 22 ℃, reaction time 0.5 hour, all the other operation conditions are the same as example 22, and the results are listed in Table 10.

Table 10 instance number catalyst Phenylacetylene conversion rate, weight % Styrene selectivity % 28 E. 4.13 100

Claims (17)

1. The catalyst is characterized by consisting of 0.15-30.00 wt% of nickel, 0.03-10.00 wt% of phosphorus, 0.01-3.50 wt% of boron and 56.50-99.81 wt% of porous carrier material, wherein the nickel exists in the form of Ni-P or Ni-B amorphous alloy and is loaded in the porous carrier material, the atomic ratio of Ni to P in the Ni-P alloy is 0.5-10.0, and the atomic ratio of Ni to B in the Ni-B alloy is 0.5-10.0.

2. The catalyst of claim 1, wherein the catalyst comprises 0.50 to 10.00 wt% nickel, 0.10 to 5.00 wt% phosphorus, 0.02 to 2.00 wt% boron, and 83.00 to 99.38 wt% porous support material.

3. The catalyst of claim 2, wherein the catalyst comprises 0.50 to 6.00 wt% nickel, 0.10 to 2.50 wt% phosphorus, 0.02 to 1.00 wt% boron, and 90.50 to 99.38 wt% porous support material.

4. The catalyst of claim 1, wherein the Ni-P amorphous alloy has an atomic ratio of Ni to P of 1.0-5.0, and the Ni-B amorphous alloy has an atomic ratio of Ni to B of 0.5-5.0.

5. A catalyst according to any one of claims 1 to 3, characterized in that the porous support material is selected from one or more of porous inorganic oxides, activated carbon, zeolites, molecular sieves.

6. The catalyst of claim 5, wherein the porous support material is silica, activated carbon or alumina.

7. The catalyst according to any one of claims 1 to 4, wherein the specific surface area of the catalyst is from 100 to 1000 m²Per gram.

8. The process for preparing the catalyst of claim 1 comprises contacting a porous support material comprising an amorphous Ni-B alloy with a porous H-containing support material at a temperature of from above the freezing point of the solution to 100 ℃₂PO₂ ^-And Ni²⁺The mixed solution is contacted and reacted; the porous carrier material containing Ni-B amorphous alloy and Ni in solution²⁺The weight ratio of (A) to (B) is 1000-1; the porous carrier material containing the Ni-B amorphous alloy comprises 0.10-20.00 wt% of the Ni-B amorphous alloy, and the atomic ratio of Ni to B is 0.5-10.0, and the preparation method comprises the steps of mixing the porous carrier material containing 0.10-20.00 wt% of Ni with BH with the molar concentration of 0.5-10.0 at the temperature of 100 ℃ higher than the freezing point of a solution₄ ^-The solution of ions is subjected to contact reaction according to the boron-nickel feeding atomic ratio of 0.1-10.0; said containing H₂PO₂ ^-And Ni²⁺H in the mixed solution of₂PO₂ ^-Has a molar concentration of 0.01 to 5.00 and Ni²⁺The molar concentration is 0.01-5.00, and the feeding atomic ratio of P to Ni in the solution is more than 0.5.

9. The method of claim 8, wherein the BH that comprises₄ ^-Ionic solutions are solutions containing BH₄ ^-Aqueous solution of ions of said BH₄ ^-The ionic precursor is selected from KBH₄Or NaBH₄Or mixtures thereof;the Ni content of the Ni-containing porous carrier material is 0.8-8.0 wt%, and the Ni-containing porous carrier material and BH₄ ^-The contact reaction temperature of the ionic solution is between room temperature and 50 ℃.

10. The method according to claim 8, wherein the porous carrier material containing the Ni-B amorphous alloy contains the Ni-B amorphous alloy in an amount of 0.5 to 8.0 wt%, and an atomic ratio of Ni to B is 1.0 to 5.0.

11. The method of claim 8, wherein the H-containing compound is₂PO₂ ^-And Ni²⁺The mixed solution of (A) means containing H₂PO₂ ^-And Ni²⁺The aqueous solution of (1), the H₂PO₂ ^-The precursor is selected from KH₂PO₂Or NaH₂PO₂Or mixtures thereof, said Ni²⁺The precursor of (a) is selected from nickel chloride or nickel acetate.

12. The method of claim 8, wherein the H-containing compound is₂PO₂ ^-And Ni²⁺The feed atomic ratio of P to Ni in the mixed solution of (1) or more is 1.0 or more.

13. The method of claim 12, wherein the P to Ni atomic ratio is 4.0 to 7.0.

14. The method of claim 8, wherein the Ni-B containing amorphous alloy porous support material is mixed with Ni in solution²⁺The weight ratio of (A) to(B) is 5 to 200.

15. The method of claim 14, wherein the Ni-B containing amorphous alloy porous support material is mixed with Ni in solution²⁺The weight ratio of (A) to (B) is 5 to 100.

16. The method of claim 8, wherein the Ni-B containing amorphous alloy porous support material is mixed with H-containing amorphous alloy₂PO₂ ^-And Ni²⁺The contact reaction of the mixed solution of (1) is carried out by directly mixing the two solutions and carrying out the contact reaction under stirring.

17. The use of the catalyst of claim 1 in hydrogenation reactions of compounds containing unsaturated functional groups.

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