CN1052668C - High-ferromagnetic non-crystalline alloy catalyst - Google Patents
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- CN1052668C CN1052668C CN95119524A CN95119524A CN1052668C CN 1052668 C CN1052668 C CN 1052668C CN 95119524 A CN95119524 A CN 95119524A CN 95119524 A CN95119524 A CN 95119524A CN 1052668 C CN1052668 C CN 1052668C
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Abstract
The present invention relates to a high-ferromagnetic non-crystalline alloy catalyst which is composed of 45 to 91 wt% of nickel, 2 to 40 wt% of iron and phosphorus as the rest, and the initial susceptibility is from 2.43 to 6.02*10<-2>emu/Oe. g. The catalyst simultaneously has the characteristics of high activity and high ferromagnetism, and the catalyst can be used as the hydrogenation catalyst of various compounds containing unsaturated functional groups and is particularly suitable for a bed reactor magnetically stabilized.
Description
The present invention relates to a kind of amorphous alloy catalyst, specifically about a kind of nickeliferous, the high-ferromagnetic non-crystalline alloy catalyst of iron and phosphorus.
Amorphous alloy is the novel catalytic material of a class, and its inner atom is a short range order, the long-range lack of alignment, and this makes its surface be evenly distributed as the atom at catalytic reaction activity center, character is identical.Result of study shows, at carbon monoxide hydrogenation (Adv.in catal 36, al36,344～357,1989) and alkene (chemical journal 47,237,1989), alkynes (J.Catal.101,67,1986) etc. contain in the hydrogenation reaction of unsaturated functional group compound, amorphous alloy catalyst all has higher activity and selectivity.But because specific surface is little, its catalytic activity is still not very good.
In order to overcome the little shortcoming of amorphous alloy specific surface, the method of various its specific surfaces of raising is arisen at the historic moment, as preparing the method (JP8611%06) of powdery Ni-P amorphous alloy, the method for mechanical powder process in the presence of at reductive agent, method (EP17308) with hydrofluoric acid treatment, change method (J.Chem Soc., Faraday Trans I, 81 that reduction is handled, 2485-2493,1985) etc., still, with the specific surface of the amorphous alloy of above-mentioned prepared in various methods also all not above 10 meters
2/ gram.For this reason, CN1073726A adopt with aluminium in advance with Ni or Fe or Co-RE-P alloying, remove wherein the method for aluminium with sodium hydroxide again through fast quenching and prepare a kind of big surface amorphous alloy, its specific surface can reach 50～130 meters
2/ gram, so huge surface-area makes the practical application of this big surface amorphous alloy become possibility.As when being used for the saturated hydrogenation reaction of alkene and aromatic hydrocarbons, its activity is apparently higher than Raney nickel catalyst (referring to CN95116430.9).
Yet, in actual application, because above-mentioned amorphous alloy catalyst particle less (20 orders are following), when being used for fixing bed, can cause too high pressure drop, and when being used for fluidized-bed, tiny granules of catalyst is easy to be taken out of by fluid, causes the loss of catalyzer.So fixed-bed process and fluidized-bed process are difficult in industrial application.When being used for batch reactor, though got rid of the above-mentioned shortcoming of fixed bed and fluidized-bed process, but batch reactor is unsuitable for the needs of scale operation, and brought the problem of catalyst separating difficulty again, therefore solve amorphous alloy, the particularly practical application of big surface amorphous alloy catalyst makes it to be suitable for more industrial production, becomes the task that this area scientific and technical personnel face.
In the sixties in this century, Filippov has proposed a kind of novel bed form.Be magnetically fluidized bed (Magnetically Fluidized Bed), the sixties are not, Tuthill (US 3440731) has proposed the notion of magnetic stablizing bed (Magnetically Stabilized Bed) on this basis again, it forms under axial, time-independent even externally-applied magnetic field effect, has only the stable bed of faint motion.Magnetic stablizing bed result of study is shown, it has some characteristic of fixed bed and fluidized-bed concurrently, both can as fluidized-bed, use the small-particle solid and be unlikely to cause too high pressure to fall loss with solid particulate, can not have tangible solid flow again as fixed bed, back-mixing has between phase and phase been controlled in the effect of externally-applied magnetic field effectively.Uniformly voidage makes bed inside not be prone to channel again, simultaneously, magnetic stablizing bed can also bubble crushing, improve mass transfer between phase and phase, and have advantages such as operation field width, stable operation, transmission effect are good.
Owing to magnetic stablizing bedly have an above-mentioned advantage, make amorphous alloy catalyst be applied to the magnetic stablizing bed possibility that becomes.
But using magnetic stablizing bed key is the solid-phase media that must have good magnetic, then must have the catalyzer that good magnetic also has greater activity simultaneously specific to magnetically stabilized bed reactor.Forefathers once imagined the magnetic that the composite grain that uses catalyzer and magnetic-particle to form increases catalyzer, adopt molecular sieve and magneticsubstance composite methods to prepare a kind of magnetic stablizing bed solid-phase media as US 4687878, EP 149343 has also adopted similar method.After having adopted catalyst activity component and iron or stainless steel or nickelalloy etc. to mix among US 4541924 and the US 4541925, prepare the catalyzer (wherein, the activity of such catalysts component is that nickel, cobalt, molybdenum, tungsten or group VIII noble metals are supported on the aluminum oxide) that has magnetic and be used for the hydrotreatment process by methods such as gellings again.But some is no any active magnetic-particle in the catalyzer that above-mentioned prepared in various methods goes out, thereby will influence original activity of such catalysts.On the other hand, existing amorphous alloy catalyst or only have advantages of high catalytic activity and do not have enough magnetic, can not be used for magnetically stabilized bed reactor separately, and the mixed volume of sneaking into the general iron powder of method of iron powder in catalyzer will account for about 16～50% of cumulative volume, this has just increased the volume of catalyzer greatly, has wasted the space (as the big surface amorphous alloy catalyst of Ni/Co-RE-P) of magnetically stabilized bed reactor; Only have enough magnetic, can be used for magnetically stabilized bed reactor separately, and not have advantages of high catalytic activity (as Fe-P, the Fe-RE-P amorphous alloy catalyst).Therefore, develop and a kind ofly both had higher magnetic and be fit to be used for magnetically stabilized bed reactor separately, the catalyzer that has higher catalytic activity again is highly significant.
Purpose of the present invention promptly is on the basis of existing amorphous alloy catalyst, and a kind of greater activity that both had is provided, and has higher ferromagnetic amorphous alloy catalyst again.
Catalyzer provided by the invention has following composition: the nickel of 45～91 heavy %, 2～40 iron that weigh and the phosphorus of surplus.
Catalyzer provided by the invention preferably consists of: the nickel of 60～91 heavy %, the iron of 2～6 heavy % and the phosphorus of surplus.
The basic parameter of sign ferromagnetic material performance quality has saturation magnetization, initial permeability and maximum permeability, situation for light current (working current is less), the magneticmedium working order is on initial one section magnetzation curve, require the initial susceptibility height of material, when catalyzer is used for when magnetic stablizing bed, consider from the energy consumption angle, should make every effort to it works under light current, therefore should adopt initial permeability to weigh the ferromagnetic property of catalyzer, and the proportional relation of magnetic permeability and susceptibility, for ease of measuring, the ferromagnetic property of catalyzer provided by the invention is represented with initial susceptibility.Catalyzer provided by the invention has high-ferromagnetic, and its initial susceptibility is 2.43～6.02 * 10
-2Emu/Oe.g, best 2.43～3.09 * 10
-2Emu/Oe.g.
Catalyzer provided by the invention can be that specific surface is 0.01～130m
2The amorphous alloy catalyst of/g is specifically:
Catalyzer provided by the invention can be that specific surface is 0.01～10m
2The amorphous alloy catalyst of/g, its preparation method can be by the described method preparation of document (Journal of Molecular Catalysis 5 (4), 272-275,1991), that is:
(1) will give in the phosphorus that adds predetermined amount after the quantitative nickel fusion, the two is alloying voluntarily, makes the Ni-P mother alloy.
(2) quantitative iron is given in adding in above-mentioned Ni-P mother alloy, refines in vacuum smelting furnace, and temperature is 1400～1500 ℃ in this stove.Use vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) the above-mentioned alloy of fast quenching then, make Ni-Fe-P amorphous alloy band, the condition of quenching is copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1400～1500 ℃ of injection temperatures.
(3) with above-mentioned Ni-Fe-P amorphous alloy band, be placed in the high pressure vessel, 300 ℃ were heated 4 hours in 8.0MPa hydrogen, made the alloy strip embrittlement, made Ni-Fe-P amorphous alloy powder through grinding
(4) with above-mentioned amorphous alloy powder 100～300 ℃ with oxygen (80ml/min) oxidation 0.5～4 hour, thereafter 300 ℃ down with hydrogen (60ml/min) reduction 0.5～4 hours, the Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst.
Above-mentioned catalyzer can also be used JP 86119606, EP 173088, J.Chem.Soc, Faraday Trans.I, and described preparation methods such as 81,2485～2493,1985 further improve its specific surface.
Catalyzer provided by the invention preferably specific surface greater than 10m
2/ g, preferably 50～130m
2The amorphous alloy catalyst of/g, it can prepare with the method that CN 1073726A discloses, that is:
(1) preparation Ni-P mother alloy will add in the quantitative phosphorus after the quantitative nickel fusion, and the two is alloying voluntarily.
(2) quantitative iron and aluminium are given in adding in above-mentioned mother alloy, make the weight of aluminium account for 50% of gross weight, refine in vacuum smelting furnace then, get the mother alloy that Ni-Fe-P and Al respectively account for 50 heavy %, are designated as (Ni-Fe-P)
50Al
50
(3) with vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) fast quenching (Ni-Fe-P)
50Al
50Mother alloy, fast quenching condition are copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1400～1500 ℃ of injection temperatures.
(4) with fast quenching gained (Ni-Fe-P)
50Al
50Place 10～25 heavy % sodium hydroxide solutions, placed 0～2 hour for 0～50 ℃, be warming up to 50～110 ℃, constant temperature is handled and was promptly got the Ni-Fe-P amorphous alloy catalyst in 1～5 hour, and wherein sodium hydroxide concentration is advisable with overweight 20～30 heavy %.
Active component nickel in the catalyzer provided by the invention can all be a non-crystalline state, this moment is with the diffuse maximum (as shown in Figure 1) of ℃ locating a broad on the XRD spectra of CuK α target mensuration in 2 θ=45, the also mixed state that can form by non-crystalline state and crystallite attitude, this moment, the XRD spectra with CuK α target mensuration was the stack of amorphous nickel and crystallite nickel XRD spectra, and promptly ℃ locating in 2 θ=45 is the stack (as shown in Figure 2) of a broad diffuse maximum and a spike.
Catalyzer provided by the invention has the high characteristics of ferromegnetism, and it is more suitable for being used for magnetically stabilized bed reactor, and the initial susceptibility of Ni-Fe-P amorphous alloy catalyst for example provided by the invention is 2.43～6.02 * 10
-2Emu/Oe.g, and Ni
67.4-La
0.4-P
12.2Big surface amorphous alloy catalyst has only 1.31 * 10
-2Emu/Oe.g.Again for example, Ni provided by the invention under the different externally-applied magnetic field effects
78.4-Fe
2.0-P
19.6The specific magnetising moment of catalyzer all is higher than Ni
87.4-La
0.4-P
12..2Big surface amorphous alloy catalyst, and the former can be used for magnetically stabilized bed reactor separately, and the latter then must mix just with the iron powder of about 30 ~ 40 volume % can be used for magnetically stabilized bed reactor.
Catalyzer provided by the invention also has advantage of high activity simultaneously.For example, when being used for the reaction of toluene hydrogenation generation methylcyclohexane, under identical reaction conditions, Ni provided by the invention
78.4-Fe
2.0-P
19.6Activity of amorphous alloy catalyst (toluene conversion 46.5 heavy %) and the Ni for preparing with same procedure
87.4-La
0.4-P
12.2Amorphous alloy catalyst (toluene conversion 47.24 heavy %) quite, and for example, when being used for the reformed oil olefine saturation hydrogenation reaction and with the Ni of same procedure preparation
87.4-La
0.4-P
12.2Amorphous alloy catalyst is compared, and uses Ni provided by the invention
78.4-Fe
2.0-P
19.6Amorphous alloy catalyst, reduce by 50 ℃ in temperature of reaction, under the situation that the reaction velocity raising is 0.7 times, the bromine valency of product has but reduced by 5%, and activity of such catalysts promptly provided by the invention is than also much higher with the Ni-La-P amorphous alloy catalyst of same procedure preparation.
Catalyzer provided by the invention also is suitable as the hydrogenation catalyst that other aromatic hydrocarbons, alkynes, nitrile, nitro-compound, carbonyl compound and carboxylic compound etc. contain the unsaturated functional group compound except that the hydrogenation reaction that is applicable to above-mentioned toluene and alkene.
Fig. 1 is that active component nickel all is the XRD spectra of amorphous nickel catalyzator.
The XRD spectra of Fig. 2 catalyzer that to be active component nickel be made up of amorphous nickel and crystallite nickel.
The following examples will the present invention will be further described.
The measuring method of the specific magnetising moment of catalyzer and initial susceptibility is as follows among the embodiment: take by weighing quantified sample, sample is placed on the 155 type vibrating sample magnetometers of Pincetoon company product, the specific magnetising moment of measuring unit weight sample under the different externally-applied magnetic field intensity is the specific magnetising moment of sample, to add magneticstrength is X-coordinate, and the specific magnetising moment is that ordinate zou is made curve.Be the initial susceptibility of this sample by this slope of a curve of initial point.
Being determined on the ASAP2400 static capacity absorption instrument of BET specific surface measured, and absorption valency matter is liquid nitrogen.
Example 1～8
The preparation of Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst.
(1) will give quantitative phosphorus and be placed on compacting in the crucible, and pour in the crucible that phosphorus is housed after will giving quantitative nickel (technical pure) fusion, nickel and phosphorus is alloying voluntarily, after the cooling the Ni-P mother alloy.
(2) quantitative iron (technical pure) and aluminium (technical pure) are given in adding in above-mentioned Ni-P mother alloy, place vacuum toggle stove then, treat to stop 10 fens kinds again after its fusion, and vacuum tightness is 10 in this stove
-2Torr, temperature are 1400 ℃, charge into argon gas to normal pressure then and make the Ni-Fe-P-Al mother alloy, and the amount that adds aluminium accounts for 50 heavy % of Ni-Fe-P-Al mother alloy, and above-mentioned Ni-Fe-P-Al mother alloy is designated as (Ni-Fe-P)
50Al
50
(3) with vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) preparation fast quenching (Ni-Fe-P)
50Al
50Mother alloy, fast quenching condition are copper roller linear velocity 30 meter per seconds, spraying pressure 0.08MPa, 1450 ℃ of injection temperatures.
(4) with the fast quenching (Ni-Fe-P) that makes
50Al
50Place to fill the sodium hydroxide solution that gives quantitative 20 heavy %, at room temperature placed 1 hour, be warming up to 80 ℃ and constant temperature 2 hours, removing pincers wherein, the Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst be designated as A～H respectively.Wherein sodium hydroxide is to aluminium excessive 30 heavy %.
Table 1 has been listed the catalyzer that makes and has been formed, BET specific surface and initial susceptibility, Fig. 1 is the XRD spectra of catalyst B, Fig. 2 is the XRD spectra of catalyzer C, XRD spectra and Fig. 1 of catalyst A, D, G are similar, XRD spectra and Fig. 2 of catalyzer E, F, H is similar, and (XRD spectra records on Japan's D/max-IIA type of science x-ray instrument, CuK α target.Ni filtering, power 40 * 30A).
Comparative Examples 1
Prepare the big surface amorphous alloy catalyst of Ni-La-P according to disclosed method among the CN107326A.
The preparation method is with example 1～8, and each amounts of components is referring to the example among the CN107326A 6, the composition of the big surface amorphous alloy catalyst of Ni-La-P that makes, and BET specific surface and initial susceptibility are listed in the table 1, and catalyzer is designated as I.
Comparative Examples 2
The Preparation of catalysts that big surface amorphous alloy of Ni-P and iron powder mix.
The preparation method of the big surface amorphous alloy of N-P does not just add iron with example 3.The Ni-P amorphous alloy that makes (is consisted of the heavy % of Ni80, the heavy % of P20, specific surface 105m
2/ g) 5.0 grams mix with 0.1 gram iron powder and promptly get this catalyzer, are designated as J.Its composition and initial susceptibility have been listed in the table 1.
The presentation of results of table 1, the initial susceptibility of catalyzer provided by the invention is apparently higher than big surface amorphous alloy catalyst, also be higher than Ni-P+Fe catalyzer that the Ni-P amorphous alloy mixes with iron powder, that composition is identical, thereby catalyzer provided by the invention is more suitable in magnetically stabilized bed reactor.
By the XRD spectra of amorphous nickel and crystallite nickel as can be known, amorphous nickel ℃ is located the diffuse maximum of a broad in 2 θ=45, crystallite nickel ℃ has been located a spike in 2 θ=45, Fig. 1 ℃ locates the diffuse maximum of a broad in 2 θ=45, illustrate in the catalyzer provided by the invention that active component nickel can all be made up of amorphous nickel.Fig. 2 ℃ locates to be made up of the diffuse maximum and a spike of a broad in 2 θ=45.It is equivalent to the stack at amorphous nickel and crystallite nickel XRD peak, illustrates in the catalyzer provided by the invention, and active component nickel can be made up of amorphous nickel and crystallite nickel again.
Table 1
Example 9
This example illustrates the ferromagnetic property of catalyzer provided by the invention.
Take by weighing 10mg catalyzer C and measure the specific magnetising moment under its different externally-applied magnetic field intensity, measurement result is listed in the table 2.
Comparative Examples 3
The explanation of this Comparative Examples, the ferromagnetic property of catalyzer provided by the invention is better than the big surface amorphous alloy catalyst of Ni-RE-P.
Take by weighing the 10mg catalyst I and measure the specific magnetising moment under its different externally-applied magnetic field intensity, measurement result is listed in the table 2.
The presentation of results of table 2, under different externally-applied magnetic field intensity, the specific magnetising moment of C all is higher than I, and the ferromagnetic property of catalyzer provided by the invention obviously is better than big surface amorphous alloy catalyst, thereby it is more suitable for being used for magnetically stabilized bed reactor.
Table 2
| Externally-applied magnetic field intensity Oe | Specific magnetising moment emu/g | |
| Catalyzer C | Catalyst I | |
| 200 300 400 500 600 800 1000 2000 3000 4000 5000 6000 7000 8000 | 4.26 5.27 5.82 6.22 6.56 7.00 734 830 8.72 8.99 9.27 9.40 9.54 9.68 | 2.79 3.93 4.59 5.25 5.57 6.39 6.72 7.87 8.36 8.85 9.02 9.18 9.34 9.51 |
Example 10
This example illustrates active surface area size provided by the invention.
The activity of such catalysts surface-area refers to the hydrogen adsorption surface-area.On the Pulse Chemiscrb 2700 chemisorption instrument that Micromeritics company produces, measure, its measuring method is: the dress quantified sample places sample tube, also made its drying in 8 hours at 50 ℃ of constant temperature with argon purge, be warming up to 250 ℃ and constant temperature and made its surface adsorption thing desorption in 2 hours, be cooled to 150 ℃ then, after treating temperature-stable, close argon gas.Feed hydrogen.Make sample inhale hydrogen 10 minutes, naturally cool to 50 ℃ then, with argon purge 1 hour, with the hydrogen that removes the sample surfaces physical adsorption and make detector count back zero, last heated sample to 300 ℃, when hydrogen began desorption, counter just had digital the accumulation.The record last reading, adopt following calculation formula to try to achieve active surface area:
Measurement result is listed in the table 3.
Comparative Examples 4
The explanation of this Comparative Examples, activity of such catalysts surface-area provided by the invention is greater than the Ni-RE-P amorphous alloy catalyst with the same procedure preparation.
Catalyst activity surface area test method is with real side 10, and just catalyzer is I, and the results are shown in Table 3.
The presentation of results of table 3, activity of such catalysts surface-area provided by the invention is higher than the Ni-RE-P amorphous alloy catalyst with the same procedure preparation, active surface area shows that greatly the amount of absorption hydrogen on the unit catalyzer is big, and hydrogen adsorptive capacity is greatly the high major cause of catalyst hydrogenation activity.
Table 3
| Example number | 10 | Comparative Examples 4 |
| Catalyst activity surface-area m 2/g | C 12.20 | I 12.07 |
Example 11～18
These embodiment illustrate the toluene hydrogenation activity of catalyzer provided by the invention.With the reaction of catalyzer provided by the invention as toluene hydrogenation generation methylcyclohexane, catalyzer is A～H, and catalyst levels is 1 gram.Be reflected in 100 milliliters of batch reactors and carry out, reaction raw materials is 50 milliliters of cyclohexane solutions that contain 30 volume % toluene, 140 ℃ of temperature of reaction, hydrogen pressure 4MPa.144 rev/mins of stirring velocitys, 14 hours reaction times.Raw material and product are analyzed with the HP5890 chromatographic instrument, and chromatographic column is the OV101 capillary column, and reaction result is listed in the table 4.
Comparative Examples 5～6
The explanation of this Comparative Examples, the toluene hydrogenation activity of catalyzer provided by the invention are higher than forms identical Ni-P+Fe catalyzer, with suitable with the Ni-RE-P amorphous alloy catalyst of same procedure preparation.
Catalyzer is I and J, and reaction raw materials and reaction conditions are with example 11～18, and reaction result is listed in the table 4.
The presentation of results of table 4 (1) catalyzer provided by the invention when the iron of 2～40 heavy % and the phosphorus of surplus, all can make the toluene hydrogenation generate methylcyclohexane at the nickel that consists of 45～91 heavy %.When the nickel that consists of 60～91 heavy %, when the iron of 2～6 heavy % and the phosphorus of surplus, the toluene hydrogenation activity of catalyzer is best.(2) catalyzer provided by the invention is when composition is close with the Ni-RE-P amorphous alloy catalyst for preparing with same procedure, and the two is quite active.(3) activity of such catalysts provided by the invention is much higher than the Ni-P+Fe catalyzer that the Ni-P amorphous alloy with same procedure preparation becomes with the iron powder flour mixed with adulterants, and for example, composition is all Ni
78.4Fe
2.0P
19.6Catalyzer, when making catalyzer with the former, toluene conversion reaches 46.54 heavy %, and when making catalyzer with the latter, toluene conversion only is 6.93 heavy %.
Table 4
| Example number | The catalyzer numbering | The heavy % of toluene conversion |
| 11 12 13 14 15 16 17 18 Comparative Examples, 5 Comparative Examples 6 | A B C D E F G H I J | 20.24 39.30 46.54 45.50 40.20 40.44 16.39 10.09 47.24 6.93 |
Example 19～20
These embodiment illustrate the application of catalyzer provided by the invention in magnetic stablizing bed.
Catalyzer C provided by the invention is used for magnetic stablizing bed olefine saturation hydrogenation reaction, used magnetically stabilized bed reactor is by the reaction tubes of 14 millimeters of internal diameters with outside reaction tubes, four internal diameters along the reaction tubes axial arranging are 55 millimeters, external diameter is 165 millimeters, highly be 35 millimeters, the number of turn is that Helmholtz (Helmhotz) coil and the corresponding direct supply of 370 circles formed (referring to application " saturation hydrogenating process for removing olefines from reforming produced oil " on the same day), reaction raw materials is that (the bromine valency is represented the content of alkene here for the reformed oil of bromine valency 3.79/100g, the measuring method of reaction raw materials and product bromine valency is referring to " petrochemical complex analytical procedure " RIPP test method, Science Press.P172～175,1990), reaction conditions and reaction result are listed in the table 5.
Comparative Examples 7
The explanation of this Comparative Examples, when catalyzer provided by the invention was used for the reformed oil olefine saturation hydrogenation reaction, its activity was apparently higher than the Ni-RE-P amorphous alloy catalyst with the same procedure preparation.
Catalyzer is I, and reaction raw materials and reaction conditions be with example 19～20, just temperature of reaction, reaction velocity (liquid reformate generates the volume space velocity of oily raw material) and externally-applied magnetic field intensity difference, reaction conditions and the results are shown in Table 5.
The presentation of results of table 5, on the one hand, catalyzer provided by the invention can be used for magnetically stabilized bed reactor separately, the Ni-RE-P amorphous alloy catalyst then must mix just with an amount of iron powder or other magnetic substances can be used for magnetically stabilized bed reactor, this can save the space of magnetically stabilized bed reactor, improves magnetic stablizing bed utilization ratio.On the other hand, when catalyzer provided by the invention is used for the reformed oil olefine saturation hydrogenation reaction, have than the higher catalyst activity of Ni-RE-P amorphous alloy with the same procedure preparation.For example, example 19 is compared with Comparative Examples 7, and temperature of reaction has reduced by 50 ℃, and reaction velocity has improved 0.7 times, and the bromine valency of product has but reduced by 53%.
Table 5
| Example number | 19 | 20 | Comparative Examples 7 * |
| Catalyst reaction temperatures ℃ reaction pressure MPa reaction velocity h -1Hydrogen-oil ratio V/V externally-applied magnetic field intensity Oe product bromine valency g/100g | 10mlC uses 100 1.0 20 100 400.1 0.25 separately | 10mlC uses 100 1.0 30 100 400.1 0.42 separately | 10ml I+5ml iron powder 150 1.0 12 100 133.8 0.53 |
*The independent use of catalyst I can not form magnetic stablizing 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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|---|---|---|---|
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|---|---|---|---|
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| CN1078095C (en) * | 1998-05-06 | 2002-01-23 | 中国石油化工集团公司 | Amorphous alloy catalyst containing nickel and phosphorus and preparation method thereof |
| WO2000066262A1 (en) * | 1999-04-29 | 2000-11-09 | China Petrochemical Corporation | A hydrogenation catalyst and its preparation |
| CN1093003C (en) * | 1999-04-29 | 2002-10-23 | 中国石油化工集团公司 | Hydrorefining catalyst and its preparation method |
| CN101274895B (en) * | 2007-03-30 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrogenation reduction method for aromatic nitro compound |
| CN109200951A (en) * | 2017-06-29 | 2019-01-15 | 刘志红 | A kind of catalytic reactor and production method |
| CN112458482B (en) * | 2020-11-18 | 2021-11-19 | 华中科技大学 | Amorphous NiFeP transition metal catalyst, preparation method and application |
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|---|---|---|---|---|
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| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
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|---|---|---|---|---|
| US4541925A (en) * | 1982-09-22 | 1985-09-17 | Exxon Research And Engineering Co. | Composition and hydrotreating process for the operation of a magnetically stabilized fluidized bed |
| US4541924A (en) * | 1982-09-22 | 1985-09-17 | Exxon Research And Engineering Co. | Composition and hydrotreating process for the operation of a magnetically stabilized fluidized bed |
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
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| CN1152475A (en) | 1997-06-25 |
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