JPS59109244A - Catalyst for conversion reaction of carbon monoxide to hydrogen and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a catalyst having high activity by incorporating alloys of composite oxides, composite carbides or the like consisting of Fe, Ni, Co, Pt, Pd, Ru, Rh, Os, Ir, Th, Sc, Y, La, Se, Pr, Nd or the like. CONSTITUTION:Alloys incorporating one kind of transition elements which belong to the VIII group such as Fe, Co, Ni, Ru; one kind of elements which belong to the IIIA such as Sc, Y, La, Ce; the IVA group elements such as Ti, Zr, Hf; the VA group elements such as V, Nb, Ta; the IIIB group elements such as Al, Ga; one kind of Si, Ge are allowed to react catalytically with a reactive gas (one kind of gas among O2, CO, NO, NO2, N2O) at 100 deg.C temp. Thus, the reaction gas is dissociated into C, O, N which are combined with the elements of III, IV, V groups to be plural systematic composite oxides, composite carbides, and composite nitrides.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst for a Co hydrogenation reaction, and more particularly, the present invention relates to a catalyst for a hydrogenation reaction used in the synthesis of CO and/or hydrocarbons and/or alcohols.

The present inventors proposed an alloy catalyst for a reduction reaction and a method for producing the same in Japanese Patent Application No. 7-92/θ6. The above proposal proposes that an amorphous alloy containing a metal in group VI and an element in group IVA be heated to a temperature not below the crystallization transition temperature of the alloy in a reducing or neutral atmosphere. Regarding the alloy catalyst for reduction reaction which is retained and crystallized, and its production method, it is expected to be used industrially as a hydrogenation catalyst from the viewpoint of hydrogen absorption ability and thermal stability. For example, Ni63Zr3
7 Hydrocarbons can be synthesized by hydrogen reduction of GO using an amorphous alloy catalyst.

Following the invention of the above-mentioned application, the present inventors further conducted research on catalysts for Co hydrogenation reaction, and as a result, they came up with the very highly active catalyst for Co hydrogenation reaction of the present invention and completed the present invention.

The catalyst of the present invention comprises Fs, NiIGo*Pt
y P(l eRu r Rh r Os F Ir
At least one selected from /i, Th, So
, Y, La, Ss*Pry'.

Ndv Ij r Sm + Er +
Gal Tb l D y + Ho
r Tu + 1Yb + Lu r Ac
+ Tt + Zr + Hf, V t
Nbr Ta *AJ + Ga r 8
1. A composite oxide, a composite carbide, or an alloy consisting of at least seven types selected from Ge, and at least seven types selected from composite nitrides, with the remainder being mainly the above-mentioned alloy.

The catalyst for Co hydrogenation reaction is characterized by comprising at least seven types of elements constituting the alloy and compounds of the elements constituting the alloy.

The present invention will be explained in detail below.

The catalyst of the present invention is a transition element (Fθ) belonging to the Vl group.

Go * Ni, Ru r Rh, Pa,
Os + Ir r Pt) or at least 7 types selected from the powers of Group IIIA (So, Y,
La, Ge + Pr + N (1+ Sm,
Eu + Ga, Tb, Dy t Ho +
Er + Tm + Yb * Lu, Ao *'
Th , Pap U ) + IV A group (Ti
, Zr * Hf ) r VA group (V p Nb
t Ta ) + mB group (Al t ea ) +
IV An alloy with at least one selected from Group B (s1*Cre) is heated with a reactive gas (O2+C
O.

It is a catalyst obtained by carrying out a catalytic reaction at at least 100°C using at least one selected from the group consisting of No+NO2*N20, and in the catalytic reaction, the reactive gas is dissociated by transition elements to become C, O, N, and thus dissociated C, O,
N combines with elements of groups J[, IV, and V to form multi-component composite oxides, composite carbides, and composite nitrides, and some also produce mono-component oxides, carbides, nitrides, and the like. In this way, internal stress is generated in the process of forming the above-mentioned composite compound, and depending on the conditions, the composite compound becomes porous due to the action of this stress. 'By the way, industrial catalysts have been determined to contain the optimum elements in order to efficiently produce the desired product.For example, nickel thread catalysts are used for steam reforming of hydrocarbons, and Fischer drop catalysts are For example, iron-based catalysts are used for the synthesis of alcohol, and Zn-Cr-Cuj catalysts are used for the synthesis of methanol. The selection of optimal elements has been determined by research efforts, and the properties of the catalyst are therefore considered to be approaching the saturation value.

there was.

In this technical situation of catalysts, the catalytic properties can be improved by using a carrier that has the ability to chemically modify catalytically active elements instead of the porous alumina-silica carrier that has been most commonly used in the past.゛.

Attempts to improve this are attracting attention. Example: ZrO2+ TiO2t Y for palladium catalyst
It has come to be known that there is a great effect when 2O3t()@203 or the like is used as a carrier. This effect is called 5M5I (Strong Metal 5upp
ort Interaction ) ``'' effect.

Composite oxide contained in the catalyst of the present invention.

Composite carbides and/or composite nitrides have a more direct interaction effect (Int,
Oration), and therefore, a greater effect is exerted. Fact 1. Catal・
? / l /4? (According to /9g/>, Pa −T
The activity increasing effect due to t02 No. 02 is Pa 810,2
On the other hand, one of the catalysts of the present invention, the Pa ''・-Zr -0 composite oxide, has a
The present inventors have newly discovered that it has an amazing activity-increasing effect of 13,000 times over -Slag.

Next, the present invention will be explained in detail using experimental data.

An amorphous alloy consisting of Pa 35 Zr 65 was prepared by a rotating disk method. In this method, molten metal having the above-mentioned composition is injected onto the cooling surface of a rotating metal disk to solidify the amorphous structure of the solution as it is. This amorphous pass alloy was in the form of a ribbon and had a thickness of 10 cm and a length of approximately cm. This ribbon was charged into a tubular reactor. The surface area of the ribbon is 0. /rn2/1 (BET+ ph781
80rption). Co(99,
9jt%) and H2 (99.9%) were used without further purification. The gas component composition at the outlet of the reaction vessel was measured using a gas chromatograph, and the catalyst structure and composition were analyzed using an X-ray diffraction spectrum.

FIG. 1 is a diagram showing the relationship between the elapsed time from the start of the experiment and the change in catalyst activity represented by GO conversion. The ratio of CO and H2 is l:sudashi, ゛lCClCC
The amount of gas flowed during the catalyst time (5 paa velocity
+Indicated as SV in the figure) is /, /X/S (hr
-1). The activity of this catalyst increases steadily,
A steady-state value is reached after 60 to 70 hours, and the value is about an order of magnitude larger than the initial activity. During this transition period, the selectivity for the main product, OH, decreased from deλ% to t6%. Ethane C2H6 and propane C31 (8) were the major products other than methane. Co2 was not detected by gas chromatography and H2O was the only oxygen-containing product.

It is known that hydrogenation of CO using a P,a catalyst produces exclusively methane. Therefore, it can be seen that the active sites in the product distribution of this catalyst are different from those of pure Pa.

Table 1 TF value of methanation catalyst i j /, tA Pa/Ti02I, 2
7 9r, A + 2.9R&n@y
Ni l 4'j l/, 7θ Table 1 is a table showing the turnover frequency (TF ) in a steady state based on the CO chemisorption amount standard. TF values from other literature are also shown in the same table.

The TF of this catalyst is 7 to 3 orders of magnitude larger than that of the supported Pa catalyst, which is 910 times larger than that of the conventional supported N1 catalyst, and even more than that of the supported Ru catalyst, which is the largest methanation active catalyst known. I understand. ``□The surface area of this catalyst increases during the reaction, but ・Amorphous l'J16
It is very small compared to the case of 3zr3'7 catalyst)
, Ni63Zr3+7 catalyst shows an increase in surface area of several orders of magnitude during the same reaction. According to these experimental results and their discussion, it is believed that some catalytically active species were formed on the catalyst surface during the transition reaction period as shown in FIG.

Figure 1 is a diagram showing an Xm diffraction spectrum.

The spectrum used in the first experiment in Figure 1 (B
) Spectrum (A) of the amorphous alloy showing a standard amorphous structure shows that it was crystallized during the reaction. However, the spectrum (B) is different from either the spectrum of Pal Zr or Pa=ZrJ original alloy. They do not match, nor do they match in any of the spectra previously reported for Pa and Zr compounds.

Therefore, the active species seems to be quite different from these,
It is also thought to be generated by some kind of reaction between Pa, Zr, and the reaction gas.

The spectrum (B) is the ゛□ of Pa and Zr reported in the literature.
Since it was not found in the spectrum of the compound, an attempt was made to experimentally determine the active species. Spectrum (C)
and (D) are amorphous P (135Zr6
□ is the spectrum of a sample prepared by processing No. 5 alloy. The crystallization temperature of this amorphous alloy (, igs
Hydrogen treatment at a lower temperature than 2AO"C has little effect on the amorphous structure. The closeness of spectra (C) and (B) indicates that the amorphous alloy is oxidized during the hydrogenation reaction. It shows that it was done.

In addition, the alloy that has been treated with oxygen beforehand exhibits a spectrum (CI), which is about % lower than the steady state high activity shown in Figure 1, but the normal N
The activity was more than 3 times that of the 1 catalyst, about 7000 times that of the normal Pa catalyst supported on 810z, and about 700 times that of the Pa catalyst supported on TtO2.

This shows that the catalyst previously treated with oxygen is similar in both activity and X-ray spectrum to the catalyst arrived at after 60 hours in FIG.

As described above, it has been shown that the amorphous P435Zr65 alloy can produce an extremely highly active Pa-Zr-〇 composite oxide catalyst under CO hydrogenation reaction conditions or under 02 single flow conditions. The cause of the formation of the composite oxide is thought to be due to the strong 02 affinity for Zr in the alloy and the dissociation of GO adsorbed during the CO hydrogenation reaction.

Figure 3 shows the reaction rates of various catalysts with various composition ratios of P(L-Zr system), and shows the reaction rate of various catalysts with various composition ratios of P(L-Zr system). It was found that the characteristics of the catalyst (indicated by the symbol Δ) are similar to those of the reaction in which the reaction was performed with the alloy in the crystalline state from the beginning without passing through the amorphous state, and the component composition of the Pa-Zr catalyst It can be seen that the change in activity due to It is assumed that this can be obtained.

Next, the present inventors calculated Pa27Hf73 (the number is 1 atom
The composition of the alloy is similarly shown in atomic %.
atm + pH 20, 1.2/ in atm gas,
Methane production reaction was carried out at 0°C, SV==t, tx 7o3 (hr-1). The relationship between the conversion rate (%') of GO and the reaction time in this case is shown in FIG. According to the figure, it can be seen that the conversion rate rapidly increases from around the reaction time IO time, that is, the activity increases, and the conversion rate reaches a steady state from around 110 hours. The presence of Pa-Hf-0 composite oxide in the catalyst after the reaction was determined by X-ray diffraction.

Admitted.

The inventors next developed Ni63Zr37 amorphous alloy 1
．． Co O0/? using 311 as a catalyst. atm
r N20, g3 atm gas, 2st”c *
Methane production reaction was carried out under SV-1, otxto5 (hr-1). 1' The results are shown in Figure 5. According to the figure, the conversion rate rapidly increased immediately after the start of the reaction, and 5
It can be seen that the conversion rate reached a steady value around 0 hours. Note that the surface area of the catalyst after the reaction increased to qm27II. The reaction was carried out at a cost of 3θO°
When it was carried out at C'□', the surface area increased even more to 30 m2/I. 1 Figure 6 is a diagram showing the X-ray diffraction spectrum of the catalyst after the reaction with the above 2sg''C, in which N12zτ intermetallic compound crystals and N1 crystals are present, as well as N1-Zr-C composite carbide. It turns out that it does.

Therefore, the present inventors conducted an experiment similar to the above after heating a Ni63Zr37 amorphous alloy in Co to sso''c, and found that the Co conversion rate increased from the S stage immediately after the start of the reaction.
The high activity after 0 hours in the figure showed the same activity.

Figure 7 shows the catalyst that reached steady activity after 60 hours in Figure 1, with the same H2ICO flow conditions and only the reaction temperature at 25f.
This is the result of measuring the reaction rate of CO by sequentially decreasing isy"ct from 'C. As shown in the figure, the activation energy E of the reaction calculated is /θOKJ/mol, which has been reported so far in this reaction system. indicates a value approximately equal to that shown in the figure. This shows that once a catalyst containing a complex oxide has reached high activity, it can be stably used as a highly active catalyst over a wide reaction temperature range.

Under the conditions shown in Fig. g, crystalline Pa35Ti65'
When the hydrogenation reaction of GO using the alloy was carried out, Pd35
Similar to Zr65*Pd27Hf73, a composite oxide was generated during the reaction, increasing the Co conversion rate, that is, the catalytic activity.

In order to produce the catalyst of the present invention, the content of the group 1-2 elements in the alloy used as its material must range from S atomic % to lamp atomic %. If the content is outside the lower or upper limit of this range, it is difficult to obtain a highly active COO hydrogenation reaction catalyst, which is the object of the present invention.

Can not. As is clear from Figure 3, the reason for this is 1.
This is because the catalyst of the present invention cannot contain a composite compound of 0 atomic % or more.

By the way, since the catalyst of the present invention exhibits high activity by containing a composite compound, it can be used not only for general reduction reactions other than the hydrogenation reaction of GO, but also as a catalyst for oxidation reactions in which metal oxides are widely used. can be used to advantage.

As described in detail above, the catalyst of the present invention is a catalyst that has a significantly high activity that far exceeds the activity limit of catalysts that have been widely used in the past, for example, for the hydrogenation reaction of Co, and the activity limit of this catalyst. Therefore, coal is now being used instead of petroleum-based raw materials.

This is a new system for advantageously using various carbon sources such as natural gas and biomass as chemical raw materials. - It is expected that it can be an extremely promising catalyst in carbon chemistry.

[Brief explanation of the drawing]

Figure 1 shows the relationship between Co water hydration reaction time and CO conversion rate using a Pd35Zr65 amorphous alloy catalyst. After being used as a catalyst in the reaction (B), the alloy was heated to θ°C in 02S.
OO treated (C), this alloy was heated in N2 at 240°C.
Figure 3 shows the X-ray diffraction spectrum of C treated for 5θ hours (D). content and reaction rate per unit area r (mat CO/1-m
2-aea), Figure 9 is a diagram showing the relationship with Pd27
Figure 1 shows the relationship between the reaction time at death and the conversion rate of CO using Hf73 alloy as a catalyst for COO hydrogenation reaction.
a35 A diagram showing the relationship between reaction time and CO conversion rate when Ti65 alloy is used as a catalyst for CO hydrogenation reaction. Figure 6 shows the relationship between Ni63Zr37 alloy and CO in Art''C in H2. Figure 7 showing the X-ray diffraction spectrum 5 of
The figure shows the same H2r Co catalyst that has reached steady activity in Figure 1.
A diagram showing the relationship between the reaction temperature and the conversion rate of CO when only the reaction temperature is lowered from COyr°C to /J9''c under flow conditions. FIG. 2 is a diagram showing the relationship between the reaction time of 1" and the conversion rate of CO when used as 1". Patent Applicant Hiroshi Inoue Aido Applicant Kendo Masumoto Applicant Hiroshi Komiyayama Attorney Mura 1) Political District 1-ψ 滌-<ot＊>htcooling0〇- Ward Quri Sotoku 1983-109244 (7) Continuation of page 1 oInt, C1,3 identification code Internal serial number C0
7C11048217-4H 271067457-4H C10K 3102 6561
-4H0 Inventor Ken Masumoto 3-8-22 Uesugi, Sendai City 0 Inventor Hiroshi Komiyama 2-10-210 Shin-Ogawa-cho, Shinjuku-ku, Tokyo 0 Inventor Akinori Yokoyama 7-3-1 Hongo, Bunkyo-ku, Tokyo Tokyo Department of Chemical Engineering, Faculty of Engineering, University Inventor: Hisamichi Kimura, Tohoku Institute of Canine Science and Metals, 2-1-1 Katahira, Sendai City ■Applicant: Ken Masumoto, 3-8-22 Uesugi, Sendai City ■Applicant: Hiroshi Komiyama, Shinjuku-ku, Tokyo Shin-Ogawamachi 2-10- 210 234-

Claims (1)

[Claims] 1. Fe p Ni y Co + Pt y P
At least one selected from a y Ru e Rh yos y Ir and Th z Sc,!
y La, + E3e, y Pr, v N67, Aj
, eSm/r Er * Ga, p Tb-t Dy
y Ho= +',, Tu l Y). Lu, t Ac r Ti t Zr * Hf s
V e N'b * Ta t゛zo ／ ／ ／
An element constituting the alloy, which contains at least 7 types selected from among composite oxides, composite carbides, and composite nitrides consisting of at least one of the following: Co comprising one or more selected from the compounds of elements constituting the alloy.
Catalyst for hydrogenation reactions. 2. Fe * Ni * Co F Pt * P
at least one selected from a t Ru e Rh v Os y Ir and Th , Sc y
Y t La s Set Pr y Na t
-In # Sm + Er * Ga
t Tb # Dy * Ho + Tu
＋ 'Yb l Lu r Ae y
Ti t Zr r Hf v V
v Nb ITa * kl + Ga t Si
02m An alloy consisting of + Ce O and at least one selected from Go + No, NO2
At least one selected from the group consisting of composite oxides, composite carbides, and composite nitrides of the alloy obtained by contact reaction at at least 100''C with a gas containing at least 7 of the following: It is characterized by containing one type of reaction product, and the remainder mainly consisting of one or more selected from the above-mentioned PA alloy, elements constituting the alloy, and compounds of elements constituting the alloy. The catalyst for Co hydrogenation reaction according to claim 1. 3. The content of at least seven selected from among composite oxides, composite carbides, and composite nitrides of the alloy is at least a little. Claim 1 or 2 which is 10 atomic %
Catalyst for Co hydrogenation reaction described in Section 3. 4. The remaining portion may include any one or more elemental elements selected from the constituent elements 1 of the alloy, and/or any oxide-carbide or nitride of the elemental element. The catalyst for Co hydrogenation reaction according to any one of claims 1 to 3, which inevitably contains at least seven types. 5. Fet Nt + Go, Pt + Pa
+ At least one selected from F(u, Rh t 0 IlzIr and Th l So *
Y HLa v So * Pr I N6 *
”'II HSm r Er l Cal Tb l
D7 t Hol Tu tYb, Lu,
Ac + Tt, Zr + Ht * V * N
b. An alloy consisting of at least 7 types selected from Ta, Al, Ga, St, and Go.
2. A composite oxide, a composite carbide, or a composite nitride of the above-mentioned alloy is produced by contacting it with a gas containing at least one of the following: CO, NO, NO2, N20, NONAKAKARA at-1t' at at least 700°C. At least 7 types are mainly formed and contained, and the remainder is mainly the above alloy, and any 7 selected from the following: - '□' Elements constituting the gold - Elements/compounds constituting the alloy.
A method for producing a catalyst for Co hydrogenation reaction comprising one or more species. 6. In the manufacturing method according to claim 5, the content of at least one selected from composite oxides, composite carbides, and composite nitrides in the alloy is at least 1
A method for producing a catalyst for Co hydrogenation reaction having a concentration of 0 atom%. 7. In the manufacturing method according to claim 5 or 6, any seven or more elemental elements selected from the constituent elements of the alloy and Or at least 7 types selected from oxides, carbides, and nitrides of the above-mentioned single elements are not allowed.
A method for producing a catalyst for a Co hydrogenation reaction that is produced automatically.