CN1052668C - High-ferromagnetic non-crystalline alloy catalyst - Google Patents

Abstract

A high-ferromagnetism amorphous alloy catalyst, the composition of the catalyst is 45-91% by weight of nickel, 2-40% by weight of iron and the balance of phosphorus, and the initial magnetic susceptibility is 2.43-6.02×10 ^-2 emu/ Oe.g. The catalyst has the characteristics of high activity and high ferromagnetism at the same time, can be used as a hydrogenation catalyst for various compounds containing unsaturated functional groups, and is especially suitable for magnetically stable bed reactors.

Description

A high ferromagnetic amorphous alloy catalyst

The invention relates to an amorphous alloy catalyst, in particular to a high-ferromagnetism amorphous alloy catalyst containing nickel, iron and phosphorus.

Amorphous alloys are a new class of catalytic materials, whose internal atoms are arranged in short-range order and long-range disorder, which makes the atoms on the surface as active centers of catalytic reactions evenly distributed and have the same properties. The research results show that in carbon monoxide hydrogenation reaction (Adv.in catal 36, al36,344～357,1989) and alkenes (Chemical Acta 47,237,1989), alkynes (J.Catal.101,67,1986) etc. In the hydrogenation reaction of compounds containing unsaturated functional groups, amorphous alloy catalysts have higher activity and selectivity. However, due to the small specific surface, its catalytic activity is still not ideal.

In order to overcome the shortcoming that the specific surface of the amorphous alloy is small, various methods to improve the specific surface have emerged, such as the method of preparing powdered Ni-P amorphous alloy in the presence of a reducing agent (JP8611% 06), mechanical manufacturing The method of powder, the method of hydrofluoric acid treatment (EP17308), the method of reduction treatment (J.Chem Soc., Faraday Trans I, 81, 2485-2493, 1985), etc., however, prepared by the above-mentioned various methods The specific surface area of the amorphous alloys also did not exceed 10 ^m2 /g. For this reason, CN1073726A adopts the method that aluminum is alloyed with Ni or Fe or Co-RE-P in advance, removes wherein aluminum with sodium hydroxide after rapid quenching to prepare a kind of large-surface amorphous alloy, and its specific surface can be Such a huge surface area makes ^the practical application of this large-surface amorphous alloy possible. For example, when used in the saturated hydrogenation reaction of olefins and aromatics, its activity is significantly higher than that of Raney nickel catalysts (see CN95116430.9).

However, in the actual application process, due to the smaller particles of the above-mentioned amorphous alloy catalyst (below 20 mesh), it will cause too high a pressure drop when used in a fixed bed, and when used in a fluidized bed, the fine catalyst Particles are easily carried out by the fluid, causing loss of catalyst. Therefore, the fixed bed process and the fluidized bed process are difficult to be applied in industry. When used in a batch reactor, although the above-mentioned shortcomings of the fixed bed and fluidized bed processes are eliminated, the batch reactor is not suitable for the needs of large-scale production, and it also brings the problem of difficult catalyst separation, so it is solved The practical application of amorphous alloys, especially large-surface amorphous alloy catalysts, to make them more suitable for industrial production has become a task faced by scientists in this field.

In the 1960s, Filippov proposed a new type of bed form. That is, Magnetically Fluidized Bed. In the late 1960s, Tuthill (US 3440731) proposed the concept of Magnetically Stabilized Bed. Formed under the action of an external magnetic field, there is only a stable bed with weak motion. The research results on the magnetically stabilized bed show that it has some characteristics of both the fixed bed and the fluidized bed. It can use small particles of solids like a fluidized bed without causing excessive pressure drop and loss of solid particles. There is no obvious solid flow like a fixed bed, and the effect of an external magnetic field effectively controls the back mixing between phases. The uniform porosity makes channeling less likely to occur inside the bed. At the same time, the magnetically stabilized bed can also break up air bubbles, improve the mass transfer between phases, and has the advantages of wide operating area, stable operation, and good transfer effect.

Due to the above-mentioned advantages of the magnetically stable bed, it is possible to apply the amorphous alloy catalyst to the magnetically stable bed.

However, the key to the application of a magnetically stabilized bed is a solid-phase medium with good magnetic properties. Specifically, a magnetically stabilized bed reactor must have a catalyst with good magnetic properties and high activity. Predecessors have envisaged using mixed particles formed by catalysts and magnetic particles to increase the magnetism of catalysts. For example, US 4687878 prepared a magnetically stable bed solid-phase medium by compounding molecular sieves and magnetic materials. EP 149343 also adopted a similar method. In US 4541924 and US 4541925, catalyst active components are mixed with iron or stainless steel or nickel alloys, and then a magnetic catalyst is prepared by methods such as gelation (wherein, the active components of the catalyst are nickel, cobalt, molybdenum, etc. , tungsten or Group VIII noble metal supported on alumina) and used in the hydrotreating process. However, some of the catalysts prepared by the above methods are magnetic particles without any activity, which will definitely affect the activity of the original catalyst. On the other hand, the existing amorphous alloy catalysts either only have high catalytic activity but not enough magnetism, and cannot be used alone in a magnetically stable bed reactor, and the method of mixing iron powder into the catalyst is generally mixed with iron powder The amount will account for about 16～50% of the total volume, which greatly increases the volume of the catalyst and wastes the space of the magnetically stable bed reactor (such as Ni/Co-RE-P large surface amorphous alloy catalyst); or only It has sufficient magnetism and can be used alone in a magnetically stable bed reactor without high catalytic activity (such as Fe-P, Fe-RE-P amorphous alloy catalyst). Therefore, it is of great significance to develop a catalyst with high magnetic properties suitable for magnetically stabilized bed reactors alone and high catalytic activity.

The purpose of the present invention is to provide an amorphous alloy catalyst with high activity and high ferromagnetism on the basis of the existing amorphous alloy catalyst.

The catalyst provided by the invention has the following composition: 45-91% by weight of nickel, 2-40% by weight of iron and the balance of phosphorus.

The preferred composition of the catalyst provided by the invention is: 60-91% by weight of nickel, 2-6% by weight of iron and the balance of phosphorus.

The basic parameters that mark the performance of ferromagnetic materials are saturation magnetization, initial permeability and maximum permeability. For the case of weak current (low operating current), the working state of the magnetic medium is on the initial section of the magnetization curve. The initial magnetic susceptibility of the material is high. When the catalyst is used in a magnetically stable bed, it should work under weak electricity from the perspective of energy consumption. Therefore, the initial magnetic permeability should be used to measure the ferromagnetic properties of the catalyst, and the magnetic permeability The ferromagnetic property of the catalyst provided by the invention is represented by the initial magnetic susceptibility for the convenience of measurement. The catalyst provided by the invention has high ferromagnetism, and its initial magnetic susceptibility is 2.43 to 6.02×10 ^-2 emu/Oe.g, preferably 2.43 to 3.09×10 ^-2 emu/Oe.g.

The catalyst provided by the present invention can be an amorphous alloy catalyst with a specific surface area of 0.01 to 130m ² /g. Specifically:

The catalyst provided by the present invention can be an amorphous alloy catalyst with a specific surface area of 0.01 to 10m ² /g, and its preparation method can be prepared according to the method described in the literature (Molecular Catalysis 5(4), 272-275, 1991), namely :

(1) Add a predetermined amount of phosphorus after melting a predetermined amount of nickel, and the two will self-alloy to obtain a Ni-P master alloy.

(2) Add a predetermined amount of iron to the above-mentioned Ni-P master alloy, and smelt it in a vacuum smelting furnace. The temperature in the furnace is 1400-1500°C. Then use the vacuum quenching method (referring to JP-A-61-212332 and Fig. 2 therein) to quickly quench the above-mentioned alloys to make Ni-Fe-P amorphous alloy strips, and the quenching condition is that the line speed of the copper roll is 20-40 m/s , injection pressure 0.05 ~ 0.1MPa, injection temperature 1400 ~ 1500 ℃.

(3) Place the above-mentioned Ni-Fe-P amorphous alloy strip in a high-pressure container, heat it in 8.0MPa hydrogen at 300°C for 4 hours to embrittle the alloy strip, and grind it to make Ni-Fe-P Amorphous alloy powder

(4) Oxidize the above amorphous alloy powder with oxygen (80ml/min) at 100-300°C for 0.5-4 hours, and then reduce it with hydrogen (60ml/min) at 300°C for 0.5-4 hours to obtain Ni-Fe -P ferromagnetic amorphous alloy catalyst.

Above-mentioned catalyst can also use the preparation method described in JP 86119606, EP 173088, J.Chem.Soc, Faraday Trans.I, 81,2485～2493,1985 etc., further improve its specific surface area.

The catalyst provided by the present invention is preferably an amorphous alloy catalyst with a specific surface greater than 10m ² /g, preferably 50-130m ² /g, which can be prepared by the method disclosed in CN 1073726A, namely:

(1) To prepare Ni-P master alloy, a certain amount of nickel is melted and then added to a certain amount of phosphorus, and the two are self-alloyed.

(2) Add a predetermined amount of iron and aluminum in the above-mentioned master alloy, so that the weight of aluminum accounts for 50% of the total weight, and then refine it in a vacuum smelting furnace to obtain Ni-Fe-P and Al each accounting for 50% by weight The master alloy is denoted as (Ni-Fe-P) ₅₀ Al ₅₀ .

(3) Rapid quenching (Ni-Fe-P) ₅₀ Al ₅₀ master alloy by vacuum quenching method (see JP-A-61-212332 and Fig. 2 therein), and the quenching condition is that the line speed of the copper roll is 20-40 m/s, The injection pressure is 0.05-0.1MPa, and the injection temperature is 1400-1500°C.

(4) Place (Ni-Fe-P) ₅₀ Al ₅₀ obtained by rapid quenching in 10-25% by weight sodium hydroxide solution, place it at 0-50°C for 0-2 hours, raise the temperature to 50-110°C, and perform constant temperature treatment for 1 Ni-Fe-P amorphous alloy catalysis can be obtained within ~5 hours, and the dosage of sodium hydroxide is preferably 20-30% by weight.

Active component nickel in the catalyzer provided by the invention can all be amorphous state, and at this moment, there is a wider diffusion peak (as shown in Figure 1) at 2θ=45 DEG C on the XRD spectrogram of measuring with CuKα target, also It can be a mixed state composed of amorphous state and microcrystalline state. At this time, the XRD spectrum measured by CuKα target is the superposition of amorphous nickel and microcrystalline nickel XRD spectrum, that is, it is a wide range at 2θ=45°C. Superposition of a diffuse peak and a sharp peak (as shown in Figure 2).

The catalyst provided by the present invention has the characteristics of high ferromagnetism, and it is more suitable for use in a magnetically stable bed reactor. For example, the initial magnetic susceptibility of the Ni-Fe-P amorphous alloy catalyst provided by the present invention is 2.43～6.02×10 ^{- 2} emu/Oe.g, while the Ni _67.4 -La _0.4 -P _12.2 large surface amorphous alloy catalyst is only 1.31×10 ^-2 emu/Oe.g. For another example, the magnetization of the Ni _78.4 -Fe _2.0 -P _19.6 catalyst provided by the present invention is higher than that of the Ni _87.4 -La _0.4 -P _12..2 large-surface amorphous alloy catalyst under the action of different external magnetic fields, and the former can be independently It is used in magnetically stabilized bed reactors, while the latter must be mixed with about 30~40% iron powder by volume to be used in magnetically stabilized bed reactors.

The catalyst provided by the invention also has the characteristics of high activity. For example, when used for the reaction of toluene hydrogenation to generate methylcyclohexane, under the same reaction conditions, the activity of the Ni _78.4 -Fe _2.0 -P _19.6 amorphous alloy catalyst provided by the invention (toluene conversion rate 46.5 wt. %) and Ni _87.4 -La _0.4 -P _12.2 amorphous alloy catalyst (toluene conversion rate 47.24% by weight) prepared by the same method is equivalent, and for another example, when used for reforming to generate oil olefin saturated hydrogenation reaction, and use Compared with the Ni _87.4 -La _0.4 -P _12.2 amorphous alloy catalyst prepared by the same method, with the Ni _78.4 -Fe _2.0 -P _19.6 amorphous alloy catalyst provided by the present invention, the reaction temperature is reduced by 50°C and the reaction space velocity is increased In the case of 0.7 times, the bromine value of the product has decreased by 5%, that is, the activity of the catalyst provided by the invention is much higher than that of the Ni-La-P amorphous alloy catalyst prepared by the same method.

The catalyst provided by the invention is not only suitable for the hydrogenation reaction of toluene and olefins, but also suitable for use as a hydrogenation catalyst for compounds containing unsaturated functional groups such as other aromatics, alkynes, nitriles, nitro compounds, carbonyl compounds and carboxyl compounds.

Figure 1 is the XRD spectrum of a catalyst whose active component nickel is all amorphous nickel.

Fig. 2 is an XRD spectrum of a catalyst whose active component nickel is composed of amorphous nickel and microcrystalline nickel.

The following examples will further illustrate the present invention.

The magnetization of catalyst in the embodiment and the measuring method of initial magnetic susceptibility are as follows: take quantitative sample, sample is placed on the 155 type vibrating sample magnetometers that Pincetoon company produces, measure the unit weight sample under different applied magnetic field intensity The magnetization intensity is the magnetization intensity of the sample, and the external magnetic field intensity is the abscissa, and the magnetization intensity is the ordinate to draw a curve. The slope of the curve through the origin is the initial magnetic susceptibility of the sample.

The determination of the BET specific surface was performed on an ASAP2400 static capacity adsorption instrument, and the adsorption valence was liquid nitrogen.

Instances 1 to 8

Preparation of Ni-Fe-P High Ferromagnetism Amorphous Alloy Catalyst.

(1) Place the predetermined amount of phosphorus in the crucible for compaction, melt the predetermined amount of nickel (industrial pure) and pour it into the crucible containing phosphorus, nickel and phosphorus will alloy themselves, and Ni-P master alloy will be obtained after cooling .

(2) Add a predetermined amount of iron (industrial pure) and aluminum (industrial pure) to the above-mentioned Ni-P master alloy, then place it in a vacuum button furnace, and wait for it to melt for another 10 minutes. The temperature is 10 ^-2 Torr, the temperature is 1400 ° C, and then filled with argon to normal pressure to obtain the Ni-Fe-P-Al master alloy, the amount of aluminum added accounts for 50% by weight of the Ni-Fe-P-Al master alloy, The aforementioned Ni-Fe-P-Al master alloy is denoted as (Ni-Fe-P) ₅₀ Al ₅₀ .

(3) Rapidly quenched (Ni-Fe-P) ₅₀ Al ₅₀ master alloy was prepared by vacuum quenching method (see JP-A-61-212332 and Fig. 2 therein), and the quenching condition was that the line speed of the copper roll was 30 m/s, spraying The pressure is 0.08MPa, and the injection temperature is 1450°C.

(4) Place the prepared quick-quenched (Ni-Fe-P) ₅₀ Al ₅₀ in a predetermined amount of 20% by weight sodium hydroxide solution, place it at room temperature for 1 hour, raise the temperature to 80°C and keep the temperature for 2 Hours, to remove the pincers, Ni-Fe-P ferromagnetic amorphous alloy catalysts were recorded as A ~ H. Wherein the excess of sodium hydroxide to aluminum is 30% by weight.

Table 1 has listed the catalyst composition that makes, BET specific surface and initial magnetic susceptibility, Fig. 1 is the XRD spectrogram of catalyst B, Fig. 2 is the XRD spectrogram of catalyst C, the XRD spectrogram of catalyst A, D, G Similar to Fig. 1, the XRD spectrum of catalyst E, F, H is similar to that of Fig. 2 (XRD spectrum is measured on the Japan Rigaku D/max-IIA type X-ray instrument, CuKα target. Ni filter, power 40 * 30A) .

Comparative example 1

According to the method disclosed in CN107326A, a Ni-La-P large-surface amorphous alloy catalyst is prepared.

The preparation method is the same as Examples 1-8, and the dosage of each component is referred to Example 6 in CN107326A. The composition of the Ni-La-P large-surface amorphous alloy catalyst, BET specific surface area and initial magnetic susceptibility are listed in Table 1. , the catalyst is denoted as I.

Comparative example 2

Preparation of Catalyst Mixed with Ni-P Large Surface Amorphous Alloy and Iron Powder.

The preparation method of the NP large-surface amorphous alloy is the same as Example 3, except that no iron is added. The catalyst was obtained by uniformly mixing 5.0 g of Ni-P amorphous alloy (composition of 80 wt% Ni, 20 wt% P, specific surface area 105 m ² /g) and 0.1 g iron powder, which was designated as J. Table 1 lists its composition and initial magnetic susceptibility.

The results in table 1 illustrate that the initial magnetic susceptibility of the catalyst provided by the invention is significantly higher than that of the large-surface amorphous alloy catalyst, and also higher than that of Ni-P amorphous alloy and iron powder mixed with the same composition of Ni- P+Fe catalyst, so the catalyst provided by the invention is more suitable for magnetically stable bed reactors.

From the XRD spectra of amorphous nickel and microcrystalline nickel, it can be seen that amorphous nickel has a broad diffuse peak at 2θ=45°C, and microcrystalline nickel has a sharp peak at 2θ=45°C. Figure 1 shows that at 2θ=45°C There is a broad diffuse peak, which shows that in the catalyst provided by the present invention, the active component nickel can be entirely composed of amorphous nickel. Figure 2 consists of a broad diffuse peak and a sharp peak at 2θ=45°C. It is equivalent to the superposition of the XRD peaks of amorphous nickel and microcrystalline nickel, indicating that in the catalyst provided by the invention, the active component nickel can be composed of amorphous nickel and microcrystalline nickel.

Table 1

Example 9

This example illustrates the ferromagnetic properties of the catalysts provided by this invention.

Weigh 10 mg of catalyst C to measure its magnetization under different applied magnetic field strengths, and the measurement results are listed in Table 2.

Comparative example 3

This comparative example shows that the ferromagnetic performance of the catalyst provided by the present invention is better than that of the Ni-RE-P large-surface amorphous alloy catalyst.

Weigh 10 mg of catalyst I to measure its magnetization under different applied magnetic field strengths, and the results are listed in Table 2.

The result explanation of table 2, under different applied magnetic field strengths, the magnetization of C is all higher than 1, and the ferromagnetic property of catalyst provided by the invention is obviously better than large surface amorphous state alloy catalyst, thereby it is more suitable for magnetic stability bed reactor.

Table 2 Applied magnetic field strength Oe Magnetization emu/g Catalyst C Catalyst I 20030040050060080010002000300040005000600070008000 4.265.275.826.226.567.007348308.728.999.279.409.549.68 2.793.934.595.255.576.396.727.878.368.859.029.189.349.51

Instance 10

This example illustrates the magnitude of the active surface area provided by the present invention.

测定结果列于表3中。The active surface area of the catalyst refers to the hydrogen adsorption surface area. Measured on the Pulse Chemiscrb 2700 chemical adsorption instrument produced by Micromeritics, the determination method is: the sample of the loaded amount is placed in the sample tube, kept at a constant temperature of 50 ° C and purged with argon for 8 hours to make it dry, then heated to 250 ° C and Keep the temperature constant for 2 hours to desorb the adsorbed substances on the surface, then lower the temperature to 150°C, and turn off the argon gas after the temperature stabilizes. Introduce hydrogen. Let the sample absorb hydrogen for 10 minutes, then cool naturally to 50°C, and purge with argon for 1 hour to remove the hydrogen physically adsorbed on the surface of the sample and make the detector count back to zero, and finally heat the sample to 300°C, and the hydrogen begins to desorb , the counter will accumulate numbers. Record the final reading and calculate the active surface area using the following formula:

The measurement results are listed in Table 3.

Comparative example 4

This comparative example shows that the active surface area of the catalyst provided by the present invention is larger than that of the Ni-RE-P amorphous alloy catalyst prepared by the same method.

Catalyst active surface area measurement method is the same as real side 10, just catalyst is 1, and the results are listed in table 3.

The result explanation of table 3, the active surface area of the catalyst provided by the present invention is higher than the Ni-RE-P amorphous alloy catalyst prepared by the same method, and the large active surface area shows that the amount of absorbing hydrogen on the unit catalyst is large, and the amount of hydrogen adsorption is large This is the main reason for the high hydrogenation activity of the catalyst.

table 3 instance number 10 Comparative example 4 Catalyst active surface area m ² /g C12.20 I12.07

Instances 11-18

These examples illustrate the toluene hydrogenation activity of the catalysts provided by the present invention. The catalyst provided by the present invention is used for the reaction of hydrogenating toluene to generate methylcyclohexane, the catalysts are A to H, and the amount of the catalyst is 1 gram. The reaction was carried out in a 100 ml batch reactor, the reaction raw material was 50 ml of cyclohexane solution containing 30 volume % toluene, the reaction temperature was 140° C., and the hydrogen pressure was 4 MPa. The stirring speed was 144 rpm, and the reaction time was 14 hours. The raw materials and products were analyzed with a HP5890 chromatographic instrument, and the chromatographic column was an OV101 capillary column. The reaction results are listed in Table 4.

Comparative example 5-6

This comparative example shows that the toluene hydrogenation activity of the catalyst provided by the present invention is higher than that of the Ni-P+Fe catalyst with the same composition, and is equivalent to that of the Ni-RE-P amorphous alloy catalyst prepared by the same method.

Catalyst is I and J, and reaction raw material and reaction condition are with example 11～18, and reaction result is listed in table 4.

The result explanation of table 4 (1) catalyst provided by the present invention can make toluene hydrogenation generate methylcyclohexane when composition is 45～91 weight percent nickel, 2～40 weight percent iron and the phosphorus of balance . When the composition is 60-91 weight percent of nickel, 2-6 weight percent of iron and the balance of phosphorus, the catalyst has the best toluene hydrogenation activity. (2) When the composition of the catalyst provided by the invention is similar to that of the Ni-RE-P amorphous alloy catalyst prepared by the same method, the activity of the two is equivalent. (3) The activity of the catalyst provided by the present invention is much higher than the Ni-P+Fe catalyst that the Ni-P amorphous alloy prepared by the same method and the iron powder mixed surface form, for example, the composition is Ni _78.4 Fe _2.0 P _19.6 When using the former as a catalyst, the conversion rate of toluene reaches 46.54% by weight, while when using the latter as a catalyst, the conversion rate of toluene is only 6.93% by weight.

Table 4 instance number Catalyst number Toluene conversion weight % 1112131415161718 Comparative Example 5 Comparative Example 6 ABCDEFGHIJ 20.2439.3046.5445.5040.2040.4416.3910.0947.246.93

Instances 19-20

These examples illustrate the use of the catalysts provided by the invention in magnetically stabilized beds.

Catalyst C provided by the present invention is used for magnetically stable bed olefin saturated hydrogenation reaction, used magnetic stable bed reactor is by the reaction tube of internal diameter 14 millimeters and outside reaction tube, four internal diameters arranged axially along reaction tube are 55mm. mm, with an outer diameter of 165 mm, a height of 35 mm, and a Helmholtz (Helmhotz) coil with 370 turns and a corresponding DC power supply (see the application for "Reformed Oil Olefin Saturated Hydrogenation Process" on the same day), The reaction raw material is the reformed oil of bromine value 3.79/100g (the bromine value here represents the content of olefins, the assay method of reaction raw material and product bromine value is referring to "Petrochemical Analysis Method" RIPP test method, Science Press. P172～175, 1990), reaction conditions and reaction results are listed in Table 5.

Comparative Example 7

This comparative example shows that when the catalyst provided by the present invention is used in the saturated hydrogenation reaction of reforming to generate oil olefins, its activity is obviously higher than that of the Ni-RE-P amorphous alloy catalyst prepared by the same method.

Catalyst is 1, and reaction raw material and reaction condition are the same as example 19～20, just reaction temperature, reaction space velocity (volume space velocity of liquid state reforming to generate oil raw material) and applied magnetic field strength are different, and reaction condition and result are listed in table 5.

The result of table 5 shows that, on the one hand, the catalyst provided by the invention can be used in magnetically stable bed reactor alone, and Ni-RE-P amorphous alloy catalyst must be mixed with an appropriate amount of iron powder or other magnetic substances to be used in A magnetically stabilized bed reactor, which can save the space of the magnetically stabilized bed reactor and improve the utilization rate of the magnetically stabilized bed. On the other hand, when the catalyst provided by the invention is used in the saturated hydrogenation reaction of reforming to generate oil olefins, it has higher catalyst activity than the Ni-RE-P amorphous alloy prepared by the same method. For example, compared with Comparative Example 7 in Example 19, the reaction temperature was reduced by 50° C., the reaction space velocity was increased by 0.7 times, and the bromine value of the product was reduced by 53%.

table 5 instance number 19 20 Comparative example 7 ^* Catalyst Reaction Temperature °C Reaction Pressure MPa Reaction Space Velocity h ^-1 Hydrogen Oil Ratio V/V Applied Magnetic Field Strength Oe Product Bromine Value g/100g 10mlC used alone 1001.020100400.10.25 10mlC used alone 1001.030100400.10.42 10ml I+5ml iron powder 1501.012100133.80.53

^* Catalyst I alone does not form a magnetically stable bed well.

Claims (8)

1. one kind is the amorphous alloy catalyst of main ingredient with nickel and phosphorus, it is characterized in that, also contains iron in this catalyzer, and it consists of the nickel of 45～91 heavy %, the iron of 2～40 heavy % and the phosphorus of surplus.

2. catalyzer according to claim 1 is characterized in that, the nickel that consists of 60～91 heavy % of this catalyzer, the iron of 2～6 heavy % and the phosphorus of surplus.

3. catalyzer according to claim 1 is characterized in that, the initial susceptibility of this catalyzer is 2.43～6.02 * 10 ^-2Emu/Oe.g.

4. catalyzer according to claim 2 is characterized in that, the initial susceptibility of this catalyzer is 2.43～3.09 * 10 ^-2Emu/Oe.g.

5. according to claim 1 or 2 or 3 or 4 described catalyzer, it is characterized in that the specific surface of this catalyzer (BET) is 0.01～130m ²/ g.

6. according to claim 1 or 2 or 3 or 4 described catalyzer, it is characterized in that the specific surface of this catalyzer (BET) is 50～130m ²/ g.

7. catalyzer according to claim 1 and 2 is characterized in that, the nickel in this catalyzer is amorphous nickel.

8. catalyzer according to claim 1 and 2 is characterized in that, the nickel in this catalyzer is made up of amorphous nickel and crystallite nickel.

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