CN1200955A - Catalyst containing Ni-P non-crystalline-state alloy, preparation method and application thereof - Google Patents

Abstract

The present invention relates to a load type catalyst containing Ni-P amorphous alloy and its preparation and application. Said catalyst comprises (wt%) 0.15-30.00% of nickel, 0.03-10.00% of phosphorus, 0.01-3.50% of boron and 56.50-99.81% of porous catalyst material, in which the described nickel is present in the form of Ni-P or Ni-B amorphous alloy, and the atom ratio of Ni and P in the Ni-P alloy is 0.5-10.0, and the atom ratio of Ni-B in the Ni-B alloy is 0.5-10.0. Said catalyst is made up by using a porous catalyst material containing Ni-B amorphous alloy and a solution containing H2PO2(-) and Ni(2+) through contact reaction at the temp. higher than freezing point of said solution. As compared with existent catalyst it possesses higher hydrogenation activity.

Description

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

The invention relates to an amorphous alloy catalyst, a preparation method and application thereof, in particular to a catalyst containing nickel-phosphorus amorphous alloy, a preparation method and application thereof.

In the research of amorphous alloy catalyst, the following two problems need to be solved: firstly, how to improve the specific surface of the amorphous alloy catalyst to improve the catalytic activity of the catalyst, and secondly, how to keep the catalyst in an amorphous state all the time in the catalytic process, that is, how to improve the thermal stability of the amorphous alloy catalyst, in order to solve the above problems, a lot of beneficial attempts have been made by the predecessors.

CN 1073726A is prepared by pre-alloying aluminum, rare earth, phosphorus and nickel or cobalt or iron, rapidly quenching, and removing aluminum from the alloy with sodium hydroxide, wherein the specific surface of the amorphous alloy catalyst can reach 50-130 m²In grams, the hydrogenation activity is higher than that of Raney Ni catalysts which are widely used in industry.

2.5M KBH was reported in journal of Catalysis 150, 434-438, 1994₄The aqueous solution is added dropwise into 0.1M nickel acetate ethanol solution under stirring at 25 ℃, 6 ml of 8M ammonia water and a large amount of distilled water are sequentially used for washing and precipitating, and the amorphous Ni-B ultrafine particle catalyst is obtained, and the specific surface of the catalyst can also reach 29.7M²In terms of/g, however, the thermal stability of such Ni-B ultrafine particles is low. It is also reported therein that an amorphous Ni-P ultrafine particle catalyst containing Ni87.0 mol% and P13.0 mol% can be prepared by heating an aqueous solution containing nickel acetate, sodium acetate and sodium hypophosphite at 90 ℃ with stirring, adjusting the pH of the solution to 11 with a NaOH solution, and washing the precipitate with ammonia water and a large amount of distilled water in this order, and that the maximum crystallization peak temperature of this Ni-P catalyst can be 394.4 ℃ but the specific surface area thereof is only 2.78 m²Per gram.

According to the Applied Catalysis37, 339-343, 1988, the method of Chemical Plating (Chemical Plating) is adopted, namely, the method containing trisodium citrate (Na)₃C₆H₅O₇) Nickel sulfate (NiSO)₄) Sodium dihydrogen hypophosphite (NaH)₂PO₂) And sodium acetate (CH)₃COONa) with a silica gel carrier, heating to 363K (about 90 ℃ C.) with stirring, maintaining the pH of the solution at 5, reacting for about 2 hours, washing the product with distilled water and drying at 340K overnight to prepare a precipitate on SiO₂The supported Ni-P amorphous alloy catalyst not only has larger specific surface (85 m)²Pergram), and has better thermal stability (the highest crystallization peak temperature is 352 ℃), so that the catalyst is a catalyst with good industrial application prospect, however, the supported Ni-P amorphous alloy catalyst has the following defects: firstly, the catalyst is prepared by mixing a silicon oxide carrier and phosphorous acidMixture of sodium dihydrogen, nickel sulfate, sodium acetate and trisodium citrateStirring and heating the mixed solution for reaction, wherein trisodium citrate and sodium acetate in the solution are used as a complexing agent of nickel ions to control the concentration of the nickel ions in the solution, and the pH value controls the reduction speed of the nickel ions and the generation speed of the Ni-P amorphous alloy, namely the control of the pH value and the existence of the trisodium citrate and the sodium acetate ensure that the generation speed of the Ni-P amorphous alloy is slower, which is beneficial to the deposition of the Ni-P amorphous alloy on SiO₂On the support, but even in this case, since the reduction reaction of nickel ions proceeds in the solution, only a small portion of the resulting Ni-P amorphous alloy can be deposited on the silica support, and most of the Ni-P amorphous alloy adheres to the wall or to the bottom of the vessel, causing the SiO to be supported thereon₂The yield of Ni-P amorphous alloy on the support is still low and non-uniform. In addition, since amorphous alloys such as Ni-B, Ni-P can be used as dihydrogen hypophosphite ion (H)₂PO₂ ^-) Catalysts for reduction of nickel ions (see J.Phys. chem. Vol.97, No.32, P850, 1993), while the amount of Ni-P amorphous alloy not deposited on the silica support is much greater than that deposited on SiO₂The amount of Ni-P amorphous alloy on the carrier further increases the deposition rate of the nickel ion reduction reaction on the wall or the bottom of the container, so that the SiO is loaded₂The yield of the Ni-P amorphous alloy on the carrier is lower. Secondly, the existence of trisodium citrate and sodium acetate complexing agent can control the reaction speed of nickel ions, thereby being beneficial to the formation of the amorphous Ni-P alloy into SiO₂Deposition on the carrier, but because of the shielding effect of the complexing agent, the reduction degree of nickel ions is also reduced, so that a part of nickel ions in the solution can not be reduced by H₂PO₂ ^-The ions are reduced, which not only causes the waste of resources, but also increases the cost of the catalyst. Third, the catalytic activity of the catalyst is still low.

Since the amorphous Ni-B, Ni-P alloy can be used as H₂PO₂ ^-The catalyst for reducing nickel ions is prepared by uniformly dispersing Ni-B or Ni-P amorphous alloy in a carrier to obtain H₂PO₂ ^-The reaction for reducing nickel ions is alwaysThe catalyst is used for catalyzing, so that the generated Ni-P amorphous alloy can be completely loaded and uniformly dispersed on the carrier, but the Ni-P amorphous alloy which is uniformly dispersed in the carrier is not available in the prior art. The research results of the rule of preparing Ni-B amorphous alloy by a chemical reduction method in J.Phys.chem.98, 8504-8511, 1993 show that divalent metal ions and a reducing agent BH₄ ^-The reaction in aqueous solution consists of three separate reactions as follows:

since the above three reactions are fast, if the carrier and the reaction solution are simply mixed together by using the prior art (such as the chemical plating method), it is difficult to ensure that the formed Ni-B amorphous alloy is loaded on the carrier, not to mention that the Ni-B amorphous alloy is uniformly dispersed on the carrier, and therefore the prior art does not have the Ni-B amorphous alloy uniformly dispersed in the carrier, and how to load the Ni-B amorphous alloy on the carrier also becomes a technical problem in the field.

In order to solve the problems of the load technology and improve the catalytic activity of the amorphous alloy catalyst, the applicant invented "a Ni-B amorphous alloy catalyst, its preparation method and application", and filed a patent application (application number 96120054.5) to the patent office at 10/15/1996. The catalyst provided by the invention comprises 0.1-30.0 wt% of Ni-B amorphous alloy and 70.0-99.9 wt% of porous carrier material, wherein the atomic ratio of Ni to B is 0.5-10.0; the porous carrier material refers to a non-oxidative porous carrier material, preferably one or more of porous inorganic oxide, activated carbon, zeolite and molecular sieve, the porous inorganic oxide refers to oxides of elements in the IIA group, IVB group, IIIA group and IVA group of the periodic table of elements, and preferably one or moreof silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide and calcium oxide; the above-mentionedThe zeolite and molecular sieve refer to various types of silicon-aluminum zeolite and heteroatom molecular sieve, 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 and the like, and the preferred porous carrier material is silicon oxide, aluminum oxide or activated carbon. The preparation method of the catalyst comprises the steps of mixing a porous carrier material containing nickel with BH with the molar concentration of 0.5-10.0 in the temperature range of being higher than the freezing point of a solution to 100 DEG C₄ ^-The ionic solution is contacted according to the boron-nickel feeding ratio of 0.1-10.0. The invention successfully solves the technical problem of Ni-B amorphous alloy loading, and prepares a novel supported Ni-B amorphous alloy catalyst. The preparation method of the catalyst abandons the traditional NH in solution₄ ^-A process for reducing nickel by impregnating a porous support material with nickel and then using BH₄ ^-The solution reduces the nickel which is uniformly distributed in the porous carrier material, and the generated Ni-B amorphous alloy can be loaded in the porous carrier material and can be more uniformly dispersed in the carrier. The Ni-B amorphous alloy catalyst prepared by the method has the activity equivalent to that of the existing Ni-La-P large-surface amorphous alloy with the highest activity. However, the prior art has not yet presented a catalyst containing a Ni-P amorphous alloy that is relatively uniformly dispersed in a carrier. The catalytic activity of the existing amorphous alloy catalyst containing Ni-P is lower than that of the amorphous alloy catalyst with Ni-La-P large surface.

The invention aims to overcome the defect of low catalytic activity of the existing Ni-P-containing amorphous alloy catalyst and provide a supported Ni-P-containing amorphous alloy catalyst with higher activity; the invention also aims to provide a preparation method of the catalyst with higher yield of Ni and the yield of Ni-P amorphous alloy loaded on a carrier, and the invention also aims to provide the application of the catalyst.

The catalyst provided by the invention comprises 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.

The preparation method of the catalyst provided by the invention comprises the step of mixing a porous carrier material containing Ni-B amorphous alloy and a porous carrier material containing H at the temperature of between the freezing point of the solution and 100 DEG C₂PO₂ ^-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.

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

The catalyst provided by the invention preferably comprises 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; more preferred compositions are: 0.50-6.00 wt% of nickel, 0.10-2.50 wt% of phosphorus, 0.02-1.00 wt% of boron and 90.50-99.38 wt% of porous carrier material.

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

According to the catalyst provided by the invention, the porous carrier material refers to a non-oxidative porous carrier material, preferably one or more of porous inorganic oxide, activated carbon, zeolite and molecular sieve; the porous inorganic oxide refers to oxides of elements in the IIA group, IVB group, IIIA group and IVA group of the element table, wherein one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, magnesium oxide and calcium oxide is preferred; the zeolite and molecular sieve refer to various types of silicon-aluminum zeolite and heteroatom molecular sieve, 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 and the like; preferred porous support materials are silica, alumina or activated carbon.

The specific surface of the catalyst provided by the invention is changed along with the size of the specific surface of the carrier, and the specific surface can be 10-1000 m²A concentration of 100 to 1000 m²Per gram.

According to the catalyst provided by the invention, the nickel as the active component can be completely in an amorphous state, and when the X-ray diffraction spectrum measured by a CuK α target has a wider diffuse scattering peak (shown as 1 in figure 1) at the temperature of 45 ℃ at 2 theta, in some cases, the peak shape of the diffusion peak is changed due to different carriers, when active carbon is used as a carrier, the peak shape of the diffusion peak is sharper (shown as 2 in figure 1), and in other cases, the diffusion peak can be covered by the diffraction peaks of the carrier at the same position (shown as 2 and 3 in figure 1).

According to the catalyst provided by the invention, the DSC curve is different according to different carriers, and one phase transition peak temperature (shown in figures 3-4) or more than one phase transition peak temperature (shown in figure 2) can be provided.

The preparation method of the catalyst provided by the invention comprises the following specific steps:

1. preparing a porous carrier material containing Ni-B amorphous alloy by the method of CN96120054.5, namely, mixing a porous carrier containing 0.10-20.00 wt% of nickel with BH with the molar concentration of 0.5-10.0 at the temperature of between the freezing point of the solution and 100 DEG C₄ ^-The solution of ions is subjected to contact reaction according to the boron-nickel feeding atomic ratio of 0.10-10.00, the solid product is washed by distilled water until no acid radical exists, and the porous carrier material containing Ni-B amorphous alloy is obtained, whereinthe Ni-B amorphous alloy contains 0.10-20.00 wt%, and the atomic ratio of Ni to B is 0.10-20.000.5～10.00；

2. Mixing a porous carrier material comprising an amorphous Ni-B alloy with a carrier material comprising H at a temperature of from above the freezing point of the solution to 100 DEG C₂PO₂ ^-And Ni²⁺The mixed solution is contacted and reacted; h in the mixed solution₂PO₂ ^-Has a molar concentration of 0.01 to 5.00 and Ni²⁺The molar concentration of the catalyst is 0.01-5.00, the feeding atomic ratio of P to NI is more than 0.50, and the solid product is washed until no acid radical exists, so that the catalyst provided by the invention is obtained.

The nickel-containing porous support material in 1 can be a commercially available nickel-containing porous support material, or nickel can be introduced into the support by a conventional method, for example, the porous support material can be prepared by impregnating the porous support material with a soluble nickel salt solution, the impregnation can also be replaced by other methods such as a kneading method, when the porous support material is zeolite or a molecular sieve or other exchangeable support materials, the introduction of nickel can also be performed by an ion exchange method, the soluble nickel salt can be selected from one or more of nickel chloride, nickel sulfate and soluble nickel carboxylate, preferably nickel chloride or nickel acetate, and the nickel content in the nickel-containing porous support material is preferably 0.8-8.0 wt%.

The nickel-containing porous support material in item 1 is preferably dried at 90 to 200 ℃ for 3 hours or more in advance.

1 said comprises BH₄ ^-The solution of (A) may be a solution containing BH₄ ^-An aqueous or alcoholic solution of (b), said BH₄ ^-The ionic precursor is selected from KBH₄Or NaBH₄Or mixtures thereof.

1 with BH₄ ^-The temperature of the ionic solution contact reaction can be carried out at the temperature higher than 100 ℃, but the reaction is generally controlled to be in the range of higher than the freezing point of the solution to 100 ℃ for saving energy sources, and is preferably controlled to be in the range of room temperature to 50 ℃; the contact reaction time depends on the reaction temperature, when the reaction temperature is higher, the reaction speed is higher, the reaction time can be shorter, when the reaction temperature is lower, the reaction speed is lower, the reaction time can be longer, and when no hydrogen is released due to the fact that a large amount of hydrogen is released in the reaction, the reaction is shownThe time of the contact reaction is the time from the start of the reaction to the absence of hydrogen evolution.

1 with BH₄ ^-The contact reaction of the ionic solution can be directly mixed with the ionic solution, or can be carried out by mixing BH₄ ^-The ionic solution is slowly added dropwise to the support material, preferably in a slowly dropwise manner.

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

2 said containing H₂PO₂ ^-And Ni²⁺The mixed solution of ions preferably contains H₂PO₂ ^-And Ni²⁺The aqueous solution of (1), the H₂PO₂ ^-The precursor is selected from KH with or without crystal water₂PO₂Or NaH₂PO₂Or mixtures thereof; the Ni²⁺The precursor of (A) is selected from soluble nickel salt, such as one or more of nickel chloride, nickel sulfate and soluble nickel carboxylate, preferably nickel chloride or nickel acetate; the feeding atomic ratio of P to Ni in the solution is preferably 1.0 or more, more preferably 4.0 to 7.0.

2 the porous support material containing the Ni-B amorphous alloy and Ni in solution²⁺The weight ratio of (A) to (B) may be 1000 to 1, preferably 5 to 200, more preferably 5 to 100.

2 the porous support material comprising an amorphous Ni-B alloy with H₂PO₂ ^-And Ni²⁺The temperature of the contact reaction of the mixed solution can be higher than 100 ℃, but the reaction temperature is generally controlled to be higher than the freezing point of the solution to 100 ℃ for saving energy, and preferably to be between room temperature and 50 ℃; the time of the contact reaction depends on the reaction temperature, when the reaction temperature is higher, the reaction speed is higher, the reaction time can be shorter, when the reaction temperature is lower, the reaction speed is lower, the reaction time can be longer, and because of H₂PO₂When the nickel ions are reduced, hydrogen is released, the reaction is finished when no hydrogen is released, and the contact reaction time refers to the time from the beginning of the reaction to the time when no hydrogen is released.

2 the porous support material comprising an amorphous Ni-B alloy with H₂PO₂ ^-And Ni²⁺The mixed solution of (A) and (B) may be directly mixed and left to stand for contact reaction, or may be mixed and then contact reaction is carried out under stirring, or H may be contained₂PO₂ ^-And Ni²⁺The mixed solution is slowly dripped into the solutionIn the porouscarrier material of the Ni-B amorphous alloy, it is preferable to carry out the contact reaction with stirring after directly mixing.

When the catalyst provided by the invention is used for hydrogenation reaction of the compound containing the unsaturated functional group, the compound containing the unsaturated functional group can be alkene, alkyne, aromatic hydrocarbon, nitro compound, compound containing carbonyl, compound containing carboxyl and nitrile. The hydrogenation reaction comprises a saturated hydrogenation reaction and a selective hydrogenation reaction, in particular to the selective hydrogenation reaction of trace acetylene in ethylene. The process conditions for the hydrogenation reaction are those which are common to each reaction.

The catalyst provided by the invention has the following advantages:

1. the catalyst provided by the invention has higher catalytic activity than that of the prior art, for example, the catalyst containing 3.98 weight percent of nickel and prepared by the invention is prepared on SiO₂A catalyst loaded with Ni-P and Ni-B amorphous alloy, a Ni-La-P large-surface amorphous alloy catalyst disclosed in CN 1073726A, and a loaded Ni-P/SiO with nickel content of 11.70 wt% disclosed in applied catalysis37, 339-343, 1988₂The catalyst, and a conventional polycrystalline nickel catalyst containing 5.0 wt% nickel were sequentially reacted at a reaction temperature of 110 deg.C, a reaction pressure of 10.0 MPa, and a gas volume space velocity of 9000 hours^-1The catalyst is used for selective hydrogenation reaction of trace acetylene in ethylene under the condition of (1), the conversion rate of the acetylene is sequentially shown as 4, 7, 8 and 9 in figure 6, which shows that the activity of the catalyst provided by the invention is far higher than that of other catalysts, even far higher than that of a large-surface amorphous alloy catalyst with the highest hydrogenation activity in the prior art, but the Ni content of the catalyst provided by the invention is far lower than that of a Ni-La-P large-surface amorphous alloy catalyst (the Ni content is 87.4 percent by weight), which further shows that,the catalyst provided by the invention is a low-nickel high-efficiency catalyst.

2. The specific surface of the catalyst can be adjusted at will, and the specific surface of the catalyst provided by the invention can be changed along with the difference of the carriers, so that the specific surface of the catalyst can be adjusted by using different carriers, and the specific surface can be 10-1000 m²Per gram, even 100-1000 m²The specific surface area of the ultrafine particle Ni-B and Ni-P amorphous alloy catalyst disclosed by the journal of Catalysis 150, 434-438, 1994 can only reach 29.7 m²Per gram and 2.78 m²Ni-P/SiO as described in Applied Catalysis37, 339-343, 1988₂Has a specific surface of only 85 m²The amorphous alloy with the largest specific surface area of Ni-RE-P large surface can only reach 130 m²Per gram.

3. The catalyst has high thermal stability, the highest crystallization peak of the catalyst can reach 434 ℃, and the Applied Catalysis37, 339-343, 1988 discloses Ni-P/SiO₂The highest crystallization peak temperature of the catalyst is only 353 ℃, and the highest crystallization peak temperature of the Ni-La-P large-surface amorphous alloy catalyst is only 278 ℃.

The preparation method of the catalyst provided by the invention comprises the steps of firstly preparing Ni-B amorphous alloy loaded on a porous carrier, and then mixing the carrier material containing the Ni-B amorphous alloy with dihydrogen phosphite (H)₂PO₂ ^-) And nickel ion (Ni)²⁺) Since the Ni-B amorphous alloy canbe used as H₂PO₂ ^-Reduction of Ni²⁺Catalyst for the reaction, so that H is initially guaranteed₂PO₂ ^-Reduction of Ni²⁺The reaction for forming the Ni-P amorphous alloy is carried out in the carrier, thereby ensuring that the Ni-P amorphous alloy formed at the beginning can be completely loaded on the surface or in the pores of the porous carrier material, and the Ni-P amorphous alloy formed along with the reaction becomes the catalyst for the reduction reaction, so that the subsequent reduction reaction is carried out only in the carrier, and the Ni-P amorphous alloy formed later can be completely loaded on the porous carrier material, and as a result, the Ni-P amorphous alloy is formedAll Ni-P amorphous alloys of (A) are supported in a porous carrier material, and Ni-P/SiO is disclosed in applied catalysis37, 339-343, 1988₂The catalyst is prepared by loading Ni-P amorphous alloy on the carrier by 20.1 wt%, and the rest is adhered to the wall or scattered at the bottom of the container. In addition, the preparation method of the catalyst provided by the invention does not use complexing agents such as trisodium citrate and the like, and nickel ions in the solution are easily oxidized by H₂PO₂ ^-The yield of nickel is greatly improved, for example, when the catalyst is prepared by the method provided by the invention, the yield of nickel can reach 21.3-98.4 wt%, and when the atomic ratio of P to Ni is controlled to be more than 4, the yield of nickel can be ensured to reach more than 50 wt%, even 98.4 wt%, while when the method disclosed by Applied Catalysis37, 339-343, 1988 is adopted, the yield of nickel is only 16.9 wt%.

FIG. 1 is an X-ray diffraction pattern of Ni-P amorphous alloy-containing catalysts with different carriers provided by the invention;

FIG. 2 is SiO₂DSC profile of supported Ni-P amorphous alloy containing catalyst;

FIG. 3 is a DSC curve of the catalyst containing Ni-P amorphous alloy with activated carbon as carrier according to the present invention;

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

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

FIG. 6 is a graph of acetylene conversion over time for the selective hydrogenation of trace amounts of acetylene in ethylene over different catalysts.

The following examples further illustrate the invention but are not intended to limit it in any way.

Examples 1 to 15

(1) Porous support material

The carrier 1 used (number Z)₁) Is coarse pore silica gel (Qingdao ocean factory product) and carrier 2 (serial number Z)₂) Is fine-pored silica gel (Qingdao ocean factory product), and carrier 3 (number Z)₃) Is granular activated carbon (product of Beijing Guanghua Wood factory), and carrier 4 (number Z)₄) Is delta-Al₂O₃delta-Al of₂O₃Is prepared from spherical alumina (from Changling catalyst factory) used as CB-8 catalyst carrier through calcining at 900 deg.C for 4 hr, and Z₁～Z₄All are 80-120 mesh particles. The above-mentioned vector Z₁～Z₄Physicochemical properties are shown in Table 1. Wherein the crystalline phase is determined by X-ray diffraction; the specific surface and pore volume were determined by the low temperature nitrogen adsorption BET method.

TABLE 1

Carrier numbering	Type of support	Specific surface area, rice2Per gram	Pore volume, ml/g	Crystalline phase
					Z1	SiO2	401	0.95	Amorphous form
Z2	SiO2	672	0.39	Amorphous form
					Z3	Activated carbon	888	0.56	Amorphous form
Z4	Al2O3	124	0.49	δ

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

Separately weighing a fixed amount of carrier Z₁～Z₄Drying at 100-150 ℃, respectively weighing quantitative nickel acetate tetrahydrate and distilled water to prepare nickel acetate aqueous solution, soaking different carriers, drying at 120 ℃ to obtain nickel-containing carriers, and respectively weighing quantitative KBH₄And formulating into an aqueous solution of KBH₄Dropwise adding the aqueous solution into a nickel-containing carrier at room temperature, immediately carrying out the reaction and releasing hydrogen, after the dropwise addition is finished, when no hydrogen is released, indicating that the reaction is finished, washing the obtained solid product with distilled water until no acid radical exists, and preparing the porous carrier material S containing the Ni-B amorphous alloy₁～S₆The amounts of the materials used in the preparation are shown in Table 2, and the contents of the Ni-B amorphous alloy inthe obtained porous support material containing the Ni-B amorphous alloy, S, are shown in Table 3₁～S₆The contents of boron and nickel are dissolved by a microwave digestion method, and the contents are measured on a Jarrel-Ash 1000 type inductively coupled plasma direct-reading spectrometer (ICP), and the specific surface and the pore volume are measured by the same method.

TABLE 2

Carrier		Nickel acetate solution		KBH4Solutions of		Obtained a catalyst comprising Ni-B carrier Numbering
							Species of	Dosage, gram	Acetic acid nickel salt tetrahydrate Dosage, gram	The amount of water is used, keke (Chinese character of 'Keke')	KBH4By using Amount, g	The amount of water is used, keke (Chinese character of 'Keke')
Z1 Z1 Z2 Z3 Z4 Z4	5.0 5.0 5.0 5.0 5.0 5.0	0.2 0.5 0.2 0.5 0.2 1.0	9.0 9.0 9.0 9.0 9.0 5.0	0.11 0.27 0.11 0.27 0.11 0.54	12.0 12.0 12.0 12.0 12.0 7.0								S1 S2 S3 S4 S5 S6

TABLE 3

Numbering of Ni-B-containing carriers	Ni-B content, wt%	Atomic ratio of Ni to B	Specific surface area, rice2Per gram
				S1	0.59	3.44	396
S2	1.57	4.63	385
				S3	0.55	1.84	652
S4	1.56	3.41	868
				S5	0.65	3.81	125
S6	3.96	1.27	129

(3) Preparation of the catalyst

Respectively weighing quantitative carrier S containing Ni-B amorphous alloy₁～S₆Respectively weighing quantitative nickel acetate tetrahydrate and sodium dihydrogen phosphite monohydrate, dissolving in quantitative distilled water to obtain mixed solution, and mixing with carrier S containing Ni-B amorphous alloy₁～S₆Respectively added into the prepared mixed solution at different temperatures,stirring, reacting immediately on the carrier, releasing hydrogen, after different time, when no hydrogen is released, indicating that the reaction is finished, washing the obtained solid product with distilled water until no acid radical is released, thus preparing the catalyst provided by the invention, wherein the serial numbers of the catalyst are A-O, the dosage of each substance and the reaction conditions in the preparation process are listed in Table 4, the yield of Ni-P amorphous alloy loaded on the carrier and the yield of nickel are given in Table 5, and the compositions and the physicochemical properties of the catalysts A-O are given in Table 6. Wherein catalysts A to L have the formula 1 shown in FIG. 1X-ray diffraction lines, catalyst M having an X-ray diffraction line as shown at 2 in FIG. 1, and catalysts N and O having an X-ray diffraction line as shown at 3 in FIG. 1.

The yield of the Ni-P amorphous alloy loaded on the carrier refers to the weight percentage of the Ni-P amorphous alloy loaded on the carrier to the total amount of the generated Ni-P amorphous alloy (including the Ni-P amorphous alloy not loaded on the carrier), the carrier is 80-120 meshes, the generated non-loaded Ni-P amorphous alloy is extremely fine (more than 200 meshes) powder, so that particles above 120 meshes and below are screened out, the content of the Ni-P amorphous alloy is respectively measured, andthe yield can be calculated according to the following formula:

yield of Ni-P amorphous alloy supported on carrier

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

The method comprises the steps of measuring the content of boron, nickel and phosphorus in a sample dissolved by a microwave digestion method on a Jarrel-Ash 1000 type inductively coupled plasma direct-reading spectrometer (ICP), measuring the X-ray diffraction line of the catalyst on a Japan science D/MAX-3A type X-ray diffractometer by using a CuK α target under the conditions that the tube voltage is 40KV, the tube current is 35mA, the emission slit (D&S) is 1 degree, the receiving slit (R&S) is 0.5 mm, and the anti-divergence slit (S&S) is 1 degree, measuring a Ni filter, and measuring the specific surface of the catalyst as before.

TABLE 4

Examples of the invention Numbering	Amorphous containing Ni-B Alloy carrier		The mixed solution is concentrated Degree, mol/l		Mixed solution Dosage in ml	P and Ni Atomic ratio	The temperature of the reaction is controlled by the temperature, ℃	the reaction time is as long as possible, time of day
									Species of	Dosage, gram	Ni2+	H2PO2 -
	1	S1	5.00	0.10									0.10	40.00	1.00	25	3
2					S1	5.00	0.10	0.20	40.00	2.00	25	3
	3	S1	5.00	0.10									0.30	40.00	3.00	25	3
4					S1	5.00	0.10	0.40	40.00	4.00	25	3
	5	S1	5.00	0.10									0.50	40.00	5.00	25	3
6					S1	5.00	0.10	0.60	40.00	6.00	25	3
	7	S1	5.00	0.10									0.70	40.00	7.00	25	3
8					S2	5.00	0.05	0.25	40.00	5.00	8	10
	9	S2	5.00	0.05									0.30	40.00	6.00	25	2
10					S2	5.00	0.05	0.35	40.00	7.00	50	1.5
	11	S2	5.00	0.05									0.40	40.00	8.00	90	1
12					S3	5.00	0.10	0.40	40.00	4.00	25	3
	13	S4	5.00	0.12									0.48	40.00	4.00	25	2
14					S5	5.00	0.14	0.56	40.00	4.00	25	3
	15	S6	5.00	0.22									0.88	40.00	4.00	25	1.5

TABLE 5

Example numbering	Yield and weight percent of Ni-P amorphous alloy loaded on a carrier	The yield of nickel is high%
			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

Example numbering	Catalyst numbering	Composition of catalyst, wt%					Specific surface area Rice and its production process2Per gram
										Ni	Form Ni-P Ni of (2)	P	B	In Ni-P alloys Atomic ratio of Ni/P
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

Ni-P/SiO₂And (3) preparing the amorphous alloy reference catalyst.

According to the method of Applied Catalysis37, 339-340, 1988, in the presence of sodium citrate (Na)₃C₆H₅O₇·H₂O)10 g/l, NiSO₄·6H₂O20 g/l, CH₃COONa 10 g/l and NaH₂PO₂·2H₂To 40 ml of the O10 g/l mixed solution was added 5 g of Z₁A carrier, stirring the mixed solutionHeating to 363K, keeping constant temperature for 2 hours, washing the solid product with distilled water until no acid radical exists, and drying at 340K overnight to obtain Ni-P/SiO₂Amorphous alloy catalyst, its number P. The catalyst contains Ni 0.6 wt% and P0.07 wt%, and SiO is loaded in the catalyst₂The yield of the above Ni-P amorphous alloy was 20.1 wt%, and the yield of nickel was 16.9 wt%.

As can be seen from the results of tables 4 to 6 and comparative example 1:

(1) the catalyst is prepared by the method provided by the invention, the generated Ni-P amorphous alloy is completely loaded in the porous carrier material, no non-loaded Ni-P amorphous alloy is generated, and Ni-P/SiO is prepared by the method of applied catalysis37, 339-340, 1988₂In the case of the amorphous alloy catalyst, most of the Ni-P amorphous alloy produced is not supported on SiO₂On a carrier, supported on SiO₂The yield of the Ni-P amorphous alloy is only 20.1 wt%, which shows that the method provided by the invention is superior to the prior art.

(2) When the catalyst is prepared by the method provided by the invention, the nickel yield can reach 21.3-98.4%, which is obviously higher than the nickel yield (16.9 wt%) obtained by the method disclosed by Applied Catalysis37, 339-340, 1988, and the method provided by the invention is also superior to the prior art. In addition, when the catalyst is prepared by the process of the present invention H₂PO₂ ^-Amount of (2) to Ni²⁺Has a greater influence on the degree of reduction of H₂PO₂ ^-With a smaller dosage, the nickel yield is lower with H₂PO₂ ^-The nickel yield increases with increasing amount, but when the atomic ratio of P to Ni in solution is greater than 4, the nickel yield follows H₂PO₂ ^-The increasing trend of the dosage is slowed down, which shows that when the atomic ratio of P to Ni in the solution is more than 0.5, the catalyst provided by the invention can be prepared, and when the atomic ratio of P to Ni is less than 4.0, the nickel yield is lower and largerAt 7.0, the raw material waste is caused, and the nickel yield is not obviously improved, so that the atomic ratio of P to Ni in the solution is reasonably controlled to be 4-7, and at the moment, the nickel yield of more than 50 wt% can be obtained under other proper conditions, and even the nickel yield of 98.4 wt% can be obtained.

(3) When the catalyst is prepared by the method provided by the invention, the reaction temperature and the reaction time can be changed within a wide range, the reaction time is less when the reaction temperature is higher, excessive energy is consumed when the reaction temperature is too high, the reaction temperature is too low, and the reaction time is too long, so that the reaction temperature can be carried out at a temperature above the freezing point of the solution and a temperature above 100 ℃, but the reaction temperature is preferably between room temperature and 50 ℃ in order to take the two aspects of the reaction time and the energy consumption into consideration.

(4) Due to Ni-B amorphous alloy pair H₂PO₂ ^-Reduction of Ni²⁺The reaction of (2) plays a role of a catalyst, so that the content of the Ni-B amorphous alloy in the carrierhas a great influence on the reaction speed, and the reaction is faster as the content of the Ni-B amorphous alloy in the carrier is higher, so that the content of the Ni-B amorphous alloy in the carrier is different, and the reaction temperature and the reaction time are also different.

Comparative example 2

Ni-P/SiO₂The amorphous alloy catalyst Q is provided by Dengjing hair, the preparation method is shown in applied catalysis37, 339-340, 1988, the catalyst contains 11.70 wt% of Ni, 1.30 wt% of P and the balance of SiO₂. The specific surface area of catalyst Q was 85 m²Per gram.

Comparative example 3

Preparing the large-surface Ni-La-P amorphous alloy reference catalyst.

A large-surface Ni-La-P amorphous alloy catalyst R having a composition of 87.4% Ni, 0.4% La and 12.2% P and a specific surface area of 91 m was prepared under the conditions and the amounts of the respective components described in example 6 of CN 1073726A²Per gram.

Comparative example 4

Preparation of polycrystalline nickel reference catalyst.

Weighing 5 g of the carrier Z₁And impregnated with 9.82 g of a nickel nitrate solution having a concentration of 8.35 wt%, dried at 100 ℃ for 4 hours, calcined at 500 ℃ for 3 hours, and then reduced with hydrogen gas at 460 ℃ for 4 hours to obtain a reference catalyst S, which contains Ni 5.0 wt% as shown by ICP analysis.

Examples 16 to 18

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

5 mg of each catalyst E, M, N was weighed, and the DSC curve and crystallization temperature weremeasured on a differential scanning analyzer (DSC) of a DuPont 2100 thermal analysis system at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere, and the DSC curves are shown in FIGS. 2 to 4 in this order.

Comparative example 5

5 mg of catalyst R was weighed out and subjected to DSC curve measurement under the conditions described in examples 16 to 18, and the results are shown in FIG. 5.

The above results show that the thermal stability of the catalyst provided by the invention is not lower than that of the existing Ni-P/SiO₂Amorphous alloy catalyst (Ni-P/SiO)₂The highest crystallization peak temperature is 353 ℃, and the catalyst provided by the inventionThe highest crystallization peak temperature of the Ni-La-P large surface amorphous alloy catalyst is higher than 350 ℃, the highest crystallization peak temperature of the catalyst taking silicon oxide as a carrier can reach 434 ℃), and the thermal stability of the catalyst is obviously higher than that of the Ni-La-P large surface amorphous alloy catalyst with the highest activity in the prior art. The above results also show that the crystallization process of the catalyst provided by the present invention may be a phase transition process or more than one phase transition process depending on the difference of the carrier material, and when the crystallization process is represented on a DSC curve, one or more than one phase transition peak appears on the DSC curve.

The following examples and comparative examples illustrate the use of the catalysts of the present invention in hydrogenation of various compounds containing unsaturated functional groups and the activity of the catalysts, the hydrogenation reactions selected were as follows:

(1) selective hydrogenation of trace acetylene in ethyleneReaction of

The seven reactions described above represent essentially all types of hydrogenation reactions for compounds containing unsaturated functional groups.

Examples 19 to 21

The following examples illustrate the use of the catalyst provided by the present invention in the selective hydrogenation of trace amounts of acetylene in ethylene and the catalytic activity of the catalyst in that reaction.

The hydrogenation reaction is carried out on a continuous micro-reactor, the inner diameter of the reactor is3 mm, the length of the reactor is 2000 mm, the used catalyst is E, M, O, the loading of the catalyst is 0.04 g, the composition of the used raw material gas is 1.65 mol percent of acetylene,95.79 mol percent of ethylene and 2.56 mol percent of hydrogen under the reaction conditions of 110 ℃ of reaction temperature, 1.0 MPa of reaction pressure and 9000 hours of gas volume space velocity^-1The gas compositions before and after the reaction were analyzed on line by gas chromatography, and when the catalyst was E, O, M, the time-dependent change curves of the acetylene conversion were shown in the order of 4, 5 and 6 in FIG. 6.

Comparative examples 6 to 8

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

The hydrogenation reaction was carried out using the same apparatus, raw materials and catalyst loading and reaction conditions as in examples 19 to 21 except that the catalysts used were different and R, Q, S in the order, and the curves of the acetylene conversion with time were shown in the order of 7, 8 and 9 in FIG. 6.

The results in FIG. 6 show that the catalytic activity of the catalyst provided by the invention is not only much higher than that of the traditional polycrystalline nickel catalyst, but also obviously higher than that of Ni-P/SiO₂The supported catalyst and the Ni-La-P large-surface amorphous alloy catalyst with the highest catalytic activity in the prior art, and meanwhile, the nickel content in the catalyst provided by the invention is far lower than that of the Ni-La-P large-surface amorphous alloy catalyst, which shows that the catalyst provided by the invention is a low-nickel high-efficiency catalyst and has incomparable superiority compared with the prior art.

Example 22

The catalyst provided by the invention is applied to the reaction of preparing methylcyclohexane through toluene hydrogenation reaction.

The hydrogenation reaction was carried out in a 100 ml batch reactor, 50 ml of a 20% by weight toluene cyclohexane solution and 0.2 g of catalyst E were added to the reactor, 4.0 MPa hydrogen was charged into the reactor, the temperature was raised to 140 ℃ and the reaction was carried out for 1 hour with a stirring rate of 64 times/min, and after cooling, the reacted mixture was taken out and analyzed by gas chromatography, and the results are shown in Table 5.

TABLE 5

Example numbering	Catalyst and process for preparing same	Conversion of toluene, weight%
			22	E	2.46

Examples 23 to 24

The catalyst provided by the invention is applied to the reaction of preparing ethylbenzene by hydrogenating styrene.

Styrene hydrogenation was carried out as in example 22, using 50 ml of styrene, at 60 ℃ and 130 ℃ for 0.5 hour, and the other operating conditions were the same as in example 22, and the results are given in Table 6.

TABLE 6

Example numbering	Reaction temperature of	Catalyst and process for preparing same	Conversion of styrene,% by weight
				23 24	60 130	E E	0.22 91.01

Example 25

The catalyst provided by the invention is applied to the reaction of preparing hexanediamine by adiponitrile reaction.

Adiponitrile hydrogenation was carried out as in example 22 using 50 ml of 15% by weight adiponitrile in ethanol at 100 ℃ for 1 hour, and the other operating conditions were the same as in example 22, and the results are shown in Table 7.

TABLE 7

Example numbering	Catalyst and process for preparing same	Adiponitrile conversion, weight%
			25	E	1.49

Example 26

The catalyst provided by the invention is applied to the reaction of preparing aniline by nitrobenzene hydrogenation.

Nitrobenzene hydrogenation was carried out in the same manner as in example 22 using 50 ml of a 20% by weight solution of nitrobenzene in isopropanol at a reaction temperature of 89 ℃ for 1 hour, and the other operating conditions were the same as in example 22, and the results are shown in Table 8.

TABLE 8

Example numbering	Catalyst and process for preparing same	Nitrobenzene conversion, weight%
			26	E	1.41

Example 27

The catalyst provided by the invention is applied to the reaction of preparing cyclohexanol by hydrogenating cyclohexanone.

The hydrogenation of cyclohexanone was carried out in the same manner as in example 22, using 50 ml of a 30% by weight cyclohexane solution of cyclohexanone as a reaction raw material, at a reaction temperature of 95 ℃ for 1 hour, and under the same operation conditions as in example 22, the results are shown in Table 9.

TABLE 9

Example numbering	Catalyst and process for preparing same	Conversion of Cyclohexanone, weight%
			27	E	0.46

Example 28

The catalyst provided by the invention is applied to the phenylacetylene hydrogenation reaction.

Phenylacetylene was hydrogenated by the method of example 22 using 50 ml of a 15% by weight cyclohexane solution of phenylacetylene as a reaction raw material, 0.2 g of a catalyst E, a reaction temperature of 22 ℃ and a reaction time of 0.5 hours, and the other operating conditions were the same as in example 22, and the results are shown in Table 10.

Watch 10

Example numbering	Catalyst and process for preparing same	Conversion of phenylacetylene, 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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