JPS62204845A - Hydrogenating catalyst of unsaturated hydrocarbon by hydrogen and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the production of catalysts, and more particularly to hydrogenation catalysts for unsaturated hydrocarbons such as olefins and dienes, and processes for their production.

BACKGROUND OF THE INVENTION Well-developed surface metallic oils comprising porous particles of a carrier (alumina, silica gel, carbon) carrying a catalytically active metal are known in the art. Also,
Metal catalysts (skeletal catalysts) with well-developed surfaces are also known (C, N, Setterf 1
elcl), “Practical practice of heterogeneous catalysts (Heteroge
Neous Catalysis in Pract
ice)” McGraw-Hr
11) Inc., New York, 19
80].

The prior art method for producing the abovementioned catalysts with highly developed surfaces consists in depositing the catalytically active metal in highly dispersed form on a particulate carrier. Furthermore, a metal catalyst with a sufficiently developed surface (skeletal catalyst) can be prepared by, for example, leaching an alloy of a catalytically active metal with aluminum, silicon, etc. [L! - (selectively cited (opt,
c t t, ) publication reference. ) The above catalyst does not have the characteristic of selective permeability to hydrogen.

These catalysts are not durable and undergo mechanical wear during operation. It is not possible to make membranes from these catalysts.

Membrane catalysts with highly developed surfaces manufactured as foils or tubes with palladium black or other metal blacks deposited on the surface are known in the art; remains from the alloy of
Smirno 7, El, Kay, Eve Novr, A, B,
Michien: 7 (VoM, Gryaznov, V, S.

Sm1rnovv t,, + K, Iv
anova, A.

PoMir;chenko), Doklacly ANSSSR
, 1970. vol, 190. P.

144].

The gJl manufacturing method of the membrane catalyst described above involves the chemical application of palladium black or other catalytically active metal (for example nickel) black onto the surface of a membrane made from a balanoum alloy, for example an alloy of palladium and silver, or tubed. or electrochemically deposited (see the above publication).

However, prior art methods do not ensure a durable coating of the membrane with palladium black or other metallic blacks. Furthermore, the use of other catalytically active metals often reduces the permeability of the membrane catalyst to hydrogen, since hydrogen and organic molecules have access to a significant portion of the membrane surface of the membrane. This is because it becomes difficult. When grown for hours in a medium of hydrogen, air and hydrocarbons,
The metallic black layer is destroyed and peeled off.

Structural metal-1ic m
Catalysts for the hydrogenation of unsaturated hydrocarbons consisting of materials made from
No. n218830, Inc.

Pat, C1, B 01 J 25100, Bulletin of Inven-ti
ons No. 24, 1967].

The method for producing the catalyst described above involves depositing a layer of catalytically active metal on the surface of the substrate, followed by coating with a layer of catalytically inactive metal such as aluminum or zinc, and
℃ to ensure interdiffusion between the catalytically active metal and the catalytically inactive metal, followed by chemical removal of aluminum or zinc from the catalytically active metal by leaching with sodium hydroxide or potassium hydroxide. It consists of collecting the The thickness of the layer of catalytically inactive metals is equal to or ten times greater than that of active metals (see the above publication).

However, the prior art methods described above use a membrane catalyst that causes the hydrogenation process to occur using active elemental hydrogen that diffuses through the membrane! Hydrogenation processes based on catalysts prepared by the above method, which cannot be used for lithography, occur by using molecular hydrogen in competitive adsorption of hydrogen and unsaturated hydrocarbons, thus also having low hydrogenation rates and poor process selection. The sex is also low.

Problems to be Solved by the Invention The present invention provides a catalyst having a highly developed porous surface but no through pores, which has high selective permeability to hydrogen and high mechanical strength of the porous layer. The present invention relates to providing a catalyst and a method for producing a catalyst having the above properties.

Means for Solving the Problems The above object was achieved by using a balan-based catalyst for the hydrogenation of unsaturated hydrocarbons.
atalyst) with 80-95% palladium and 5-20% by weight! % of an alloy of ruthenium or ronium and comprising a non-porous layer and a porous layer disposed on one or both sides of the non-porous layer, the area of the porous surface is equal to or greater than the membrane surface. 150 holes per 1G2
This is achieved by providing a catalyst according to the invention in the range of 820 cm2 and with a thickness ratio of porous layer to non-porous ff layer of 1:5 to 1:1.000, respectively.

The above objective is also to deposit the catalytically inactive metal on the catalytically active metal, to hold these metals at a temperature that ensures their interdiffusion, and then to separate the catalytically inactive metal from the catalytically active metal. A method for producing the above catalyst by chemically recovering a
% by mass of ruthenium or ronium, copper or mercury as the catalytically inert metal, and the thickness ratio of the catalytically inert metal to the metal is 1:10.
~1:100, applied to the membrane surface on one or both sides of the membrane. When copper is used as a catalytically inactive metal, the membrane on which copper is precipitated must be heated at a temperature of 300 to 800°C. Chemical removal of copper from the membrane by holding at temperature and treatment with trichloroacetic acid; when mercury is used as the catalytically inert metal, the membrane with mercury precipitated is heated at -10 to 150 °C. Maintain temperature and 40-60%
It is also achieved by a manufacturing method consisting of chemical removal of mercury from the membrane by treating the membrane with an aqueous iron chloride solution or a 20-30% aqueous nitric acid solution.

By the method of the present invention, a highly developed porous surface with no through pores (pores (ρore) per 1 cs+2 membrane surface)
s) up to 800 α2), thus making it possible to create a decatalyst that increases the catalyst productivity during the hydrogenation process of unsaturated hydrocarbons by the use of elemental hydrogen. The selective permeability to hydrogen also increases.

Thus, the hydrogen permeability of the decatalyzed products prepared by the method of the invention is 5 to 10 times higher at room temperature (18-25° C.) than in the case of prior art decatalyzed products. For this reason,
It is possible to use the decatalyzed catalyst produced by the method of the invention in hydrogenation processes of unsaturated hydrocarbons with hydrogen at low temperatures (20-40'C). Furthermore, the porous layer of the catalyst produced by the method of the invention has high mechanical strength and is not destroyed during decatalyst operations and regeneration.

As already mentioned above, as the catalytically active metal, 80 to 9
An alloy consisting of 5% by weight of palladium and 5-20% by weight of ruthenium or ronium is used. The use of alloys with an ungrooved paranoum content of 80% by weight is not preferred since the permeability of such alloys to hydrogen is very low. On the other hand, at palladium contents above 95% by mass, the alloy becomes unstable in a hydrogen atmosphere;
Becomes easily destroyed.

The area of the porous surface for decatalyst is 7c per cm2 of membrane surface.
Pores smaller than 150 cM2 are also not recommended as such decatalysts only have low activity. At values of the area of the porous surface exceeding 820 α2 pores per cm2 of membrane surface, the porous layer becomes disintegrated.

Porous lIJ layer vs. non-porous′! The thickness of the i-layer increases to a value greater than 5, the mechanical strength of the decatalyst decreases.

If the thickness ratio of the layers is reduced to values below 1:1,000, the resulting decatalyst has only low activity and is therefore unsuitable.

The use of catalytically inert layer to layer thickness ratios of greater than 1:10 is not recommended as the high content of catalytically inert metals causes through-porosity formation in the membrane. An Irl ratio of less than 1:100 results in slight loosening of the membrane surface, which makes it impossible to produce highly active hydrogenation catalysts.

It is undesirable for the residence temperature of a film with a layer of copper to exceed 800°C, since at temperatures above 800°C deep diffusion of copper into the surface layer of the palladium alloy will occur.
This is because it becomes impossible to remove copper sufficiently in the subsequent treatment with trichloroacetic acid, and this residual copper gives a harmful effect to the activity of the membrane catalyst. 300°
If it is less than C, the diffusion of copper into the palladium alloy becomes very slow and no porous layer is formed due to the dissolution of copper by the acid.

The processing temperature for membranes with a mercury layer is limited to the range -10 to 150C for the same reasons as for membranes with a copper layer.

Trichloroacetic acid is used to dissolve the copper that has diffused into the membrane. This solvent reacts with copper but does not interact with the catalytically active palladium, ruthenium and rhodium, making it possible to obtain membrane catalysts with a porous structure on the surface.

The use of dilute nitric acid solutions is not recommended, since nitric acid with a concentration of less than 20% will only slightly dissolve the mercury. On the other hand, at a nitric pH concentration exceeding 30%, not only palladium but also ruthenium and rhodium mixed in the catalyst begin to dissolve.6 For the same reason, the selection range of the iron(III) chloride aqueous solution concentration is determined.

Working hydrogenation membrane catalysts comprise membranes shaped as foils, plates or tubes. This membrane is made from an alloy of palladium and ruthenium or rhodium and consists of a porous layer and a non-porous layer. The porous layer can be placed on both sides of the non-porous layer and on one side thereof. When placed on one side, the hydrogenation process is porous′! It should be done on the side of the trash. The thickness ratio of the porous layer to the non-porous layer ranges from 1:5 to 1:1.000, respectively. The area of the porous surface is 15 pores per IC212 of the membrane catalyst surface.
0 to 820C112.

The membrane catalyst of the present invention is manufactured as follows.

First of all, from an alloy of palladium and ruthenium or rhodium, a thin layer of copper or mercury is applied from 1:10 to 1:1 on one or both sides of the clean surface of the membrane, for example shaped as a foil, plate or tube. A catalytically inert metal layer thickness ratio of 100 is applied. Copper, for example, is subjected to vacuum atomization.
The mercury can be applied to the membrane by , electroplating, diffusion welding, preferably by dipping or casting (ca.
sting). If the applied membrane of copper or mercury is heated to a certain temperature (gliI),
300-800'C [pronation, -10 to 1 for mercury]
50° C.) and then placed in a suitable solvent. For copper, use trichloroacetic acid, for mercury, use 40-60% iron(III) chloride aqueous solution or 20-3
Use 0% nitric acid aqueous solution. After drying, a membrane catalyst with a porous layer is obtained.

The membrane catalyst 51 left as described above is tested for hydrogen permeability by the direct-flow method using a thermal conductivity cell-Kathalometer.

1. To carry out the hydrogenation process of unsaturated hydrocarbons such as 3-pentanoene, pentene, and cyclopentadiene,
The membrane catalyst of the present invention is placed in a reactor so as to partition the interior space of the reactor into two chambers. Hydrogen is supplied into one chamber and the compound to be hydrogenated is supplied into the other chamber. Hydrogen diffuses in active elemental form through the membrane catalyst into another chamber and reacts with the material to be hydrogenated at the porous surface of the membrane catalyst to form the desired product. Catalyst composition is determined by chromatography. The thickness of the porous and non-porous layers of the catalyst is determined by electron spectroscopy.

EXAMPLES In order to better understand the invention, several specific examples are set forth below that illustrate particular embodiments of the invention.

Example 1 A 1004 foil made from an alloy consisting of 90.2% palladium and 9.8% ruthenium was degreased, rinsed with distilled water and a 2 cm thick layer of copper was deposited by vacuum atomization. Applied to both sides of the foil.

The foil to which the copper layer was applied was heated to a temperature of 800° C. and then held at this temperature for 3 hours. The foil was then cooled and kept in trichloroacetic acid until sufficient copper was recovered. A decatalyst was thus obtained which was molded as a foil from the above alloy and consisted of 95 non-porous Y1 layers and superficially porous layers each having a thickness of 24 mm. B
ET (Brunauer S, + Em
mett P, H.

The area of the porous surface, measured by the Teller E.) method, was 82012 pores per cm2 of membrane surface.

The hydrogen permeability (J) of the decatalyzed catalyst prepared as described in Example 1 and the hydrogen permeability of the initial foil (not treated according to the invention) are given in Table 1 below. show.

Table 1 Temperature ('C) 200 300 350 400 As is clear from the above data, after treatment according to the invention, the permeability of the membrane to hydrogen increases by a factor of 2, Example 2 80% palladium and 20% by weight Both sides of a 50ρ foil made from an alloy consisting of
0.5/JlrPi, Sanoti4N! respectively as described in ! coated with i. 300% copper layer applied foil
Copper was then removed from the membrane by dissolving the copper in trichloroacetic acid.
The thickness of the non-porous tube layer is 494, and the thickness of each of the porous layers is F7.
′! - is 0.2. Met.

The area of the porous surface for decatalyzing was 410 cs2 per 1 cm2 of the membrane surface. The permeability to hydrogen of the decatalyst at a temperature of 350°C is 15. I X 10-'c
m2・C(-'・MP n-0st'a-) h.

Example 3 External diameter 1 made from an alloy with the same composition as in Example 1 above.
2 m and the external surface of the tube with a wall thickness of 1004 ft.
1. coated with a copper layer. 550
It was held at a temperature of 'C for 2 hours. After removing the copper by treatment with trichloroacetic acid, the above alloy was prepared and 9
A decatalyst in the form of a tube was obtained with a wall consisting of a 9N thick non-porous tube inner layer and a 1-thick perforated tube outer layer. The area of the porous surface for decatalyst is 6 pores per 1 cg12 of membrane surface.
It was 20α2. The permeability to hydrogen at a temperature of 350°C is 7.5X10-'cm2・s-'・MPa
-” was.

Example 4 0.5% on a 100% tube made from an alloy consisting of 90.2% palladium and 9.8% ruthenium
Apply thick copper foil and heat at 300℃ for 10 hours.
It was compressed under a pressure of 0.2 MPa.

In Hidden, two metals were joined together by diffusion welding. After cooling the foil consisting of metal 2!11, the copper was removed by dissolving it in trichloroacetic acid. A decatalyst in the form of a foil was obtained which was made from the above foil and consisted of a 98 mm thick non-porous layer and a 2/l thick porous layer. The area of the decatalyzed porous surface was 740 cm2 of pores per IC112 of membrane surface. The hydrogen permeability of the catalyst at a temperature of 200°C is 5,
7 X 10-'α2・1g −+ −M p a −
Oj, and the hydrogen permeability of the catalyst at a temperature of 300° C. was 11.0×10−4α2·s−1·MPa−05.

Example 5 A mercury layer of 4 cm thick was applied to each side of a 100-mm inlet made from an alloy consisting of 90.2% by weight palladium and 9.8% by weight ruthenium.

holding the foil to which the mercury layer has been applied at a temperature of 60°C for 5 hours;
Then, place it in a boiling @ 60% iron chloride (DI) aqueous solution,
The foil was kept in the solution until the mercury was completely dissolved and washed with distilled water until no reaction to chloride ions was observed. After such treatment, it consists of a non-porous layer made of the above alloy and having a thickness of 92/4, and superficially porous layers placed on both sides of this non-porous layer, each having a thickness of 4/Jl. A membrane catalyst was obtained as a foil. The area of the porous surface of the membrane catalyst was 520 cm 2 of pores per 1 cm 2 of the membrane surface.

Table 2 provides data on the hydrogen permeability of the catalyst xied according to Example 5.

Table 2 Temperature ("C) 200 300 350 400 Example 6 1000 u plates made of an alloy consisting of 92[i% palladium and 8% by mass rhodium] were each treated according to the procedure described in Example 5 above. A 5 pm thick layer of water IItM was applied. The plate to which the water layer was applied was kept at a temperature of -10°C for 3 days. The mercury was then recovered from the plate and boiled 40% iron chloride (m) treated with an aqueous solution. Thus,
A membrane catalyst was obtained as a plate made of the above alloy and consisting of a non-porous i-waste of 999 nFJ and a superficially porous layer placed on both sides of this layer, each having a thickness of 0.5 shoulders.

The value of the porous surface of the membrane catalyst is 1 pore per 102 isurfaces.
The hydrogen permeability at a temperature of 350'C was 12.9X10-4α2・s-1・MPa''
'Met.

Example 7 94% by mass palladium and 6'f! 84 mercury layers were applied on each side of a 100P11-thick foil made from an alloy consisting of i% ruthenium and
t) + oci of casting). The plate on which the mercury layer was deposited was kept at a temperature of 150°C for 1 hour. Thereafter, mercury was removed by treating the membrane with a 50% aqueous iron(III) chloride solution. The membrane catalyst is then made of the above alloy and consists of a non-porous layer of 98 P1 thickness and superficially porous layers placed on both sides of this layer, each having a thickness of 1 P1. was gotten.

The area of the porous surface of the ll catalyst was 280 CM'' pores per cm2 of m surface, and the hydrogen permeability at a temperature of 350°C was 14.I X 10-' C112 s-'
・MPa-”.

Example 8 A membrane catalyst was prepared from an alloy consisting of 95% by weight of palladium and 5% by weight of lono□ium as described in Example 7 above! However, the mercury was removed by placing the foils in aqueous nitric acid solutions of various concentrations after heat treatment at 150°C.

The thickness values of the non-porous layer and the porous layer, the area of the porous surface and the hydrogen permeability (at a temperature of 350°C) of the obtained membrane catalyst were determined as follows in relation to the concentration of nitric acid used:
Shown in the table.

Table 3 Concentration of nitric acid aqueous solution, % 20 25
30 each hole JM thickness, shore 2 3.
5 5 Thickness of non-porous layer, 74 85
70 50 Porous surface area, pores cm2/32310 450 480 Hydrogen permeability, JX104, cm'・s-'・MPa-" 12,6 14
．． 8 13.2 Example 9 On both sides of a 9004 thick plate made from an alloy having the same composition as in Example 1 above, a mercury layer of 5PR each was applied by dipping. The plate with the mercury layer thus applied was kept at a temperature of 10° C. for 24 hours, and after this residence the plate was placed in a 20% aqueous nitric acid solution for 1 hour. Thus, a non-porous layer of 900 mri left from the above alloy was deposited on both sides of this non-porous layer, each having a thickness of 0.4 mm.
A plate-shaped decatalyst consisting of a superficially porous layer with a thickness of 57q was obtained.

The area of the porous Ifltt surface is 7L250cx2 per membrane contact V & surface ICII'', and the hydrogen permeability at a temperature of 350℃ is 13.4X10-'cm2・s-'・MP
It was a-”.

Example 10 100 leftover from an alloy of the same composition as in Example 1
A mercury layer of 10/4 thickness each was applied to both sides of the - foil. The foil on which the mercury layer had been deposited was kept at a temperature of 145° C. for 1 hour. After cooling, the box was placed in a 60% aqueous iron(I) chloride solution and kept at reflux. Hidden is a foil-shaped sheath made of the above-mentioned alloy and consisting of a non-porous layer of 964 mm thick and superficially porous layers placed on both sides of this non-porous layer, each having a thickness of 24 mm. A catalyst was obtained. The area of the porous surface was 540 α2 pores per cm2 of decatalyzed surface.

Hydrogen permeability at a temperature of 300°C is 7.9X10-'
cm2・s-'・MPa-05, and at a temperature of 400℃, 13.2 X 10-' cs2・a-1・MPa
A- It was a residence.

Effects of the Invention As is clear from the above examples, the hydrogen permeability of the decatalyzed hydrogen permeable steel significantly increased compared to the initial foil (1.5~
(by a factor of 2), which makes it possible to increase the productivity of decatalyst in the hydrogenation reaction of unsaturated hydrocarbons.

Examples 11 to 16 described below are the decatalysts and gays of the present invention prepared as described in Examples 1, 2, 3, 5, and 8 above. M, Gryazno7, Kay.

Nis, Smirno 7, El, Kay, Eve 7/Vua, Ei,
Bi, Michien: 7 (V, M, Gryaznov.

V, S, Sm1rnov, L, K, Ivano.
DokladyAN 5SSR 1970゜vol.
, 190. 144 shows a prior art decatalytic hydrogenation process for unsaturated hydrocarbons produced by the method described in 144.

Example 11 A study of the catalytic properties of a decatalyst shaped as a tube according to Example 3 was carried out by hydrogenating 1,3-pentanoene in a reactor separated into two chambers by said decatalyst. In one chamber formed by the tube cavity, hydrogen was fed at a rate of 30 d/min, and in the other chamber formed by the outer surface of the reactor wall upstream tube, 1,3-pentanoene and A mixture with argon was fed under a vapor pressure of 10 wHg of 1,3-pentanoene at a rate of 10 d/min.

Catalytic reaction products obtained at various hydrogenation temperatures (catalytic reaction products)
The composition of lysate) is shown in 4 & below.

Table 4 Ten Ten Diene 60 63.0 - 1,1 35.91
00 77.9 0.1 12,0 10,0
180 82.5 1.3 2.2 14.
Example 12 The study of the catalytic properties of the membrane catalyst prepared as a foil in accordance with Example 5 above was carried out by hydrogenating 1,3-pentanoene in a reactor partitioned into two chambers by the above catalyst. In one chamber, hydrogen flow was supplied at a rate of 30 d/min and in the other chamber, 1.3 d/min.
- Pentadiene vapor was fed into the argon stream at a rate of 75 d/min under a hydrocarbon vapor pressure of 15 ztl.

The composition of the catalytic reaction products obtained at various hydrogenation temperatures is shown in Table 5 below.

Table 5 Pentane 1-Pentene 2-Pentene 100
11.3 15.9 72.8110
13.1 16.8 70,1150
20.9 6.4 72.7 cases
13 A study of the catalytic properties of the membrane catalyst produced in the form of a foil according to Example 2 above was carried out by hydrogenating 1,3-pentadiene in a reactor partitioned into two chambers by the above catalyst. Hydrogen was supplied into one chamber at a rate of 30 d/min, and into the other chamber at 1,3 d/min.
- Pentanoene vapor was fed into the argon stream at a rate of 30 d/min under a hydrocarbon vapor pressure of 15 wilg.

The composition of the catalytic reaction products obtained in the hydrogenation steps carried out at various temperatures is shown in the PIS 6 table below.

Table 6 Pentane 1-Pentane 2-Pentane 100
14.9 9.6 75.5110
32.0 4.0 64.0150
25.0 5.4 69.6 cases 14 (
Comparative example) Gui. M, Gryaz/7, gay. Varnish, Smil/7,
L, Kay, Eve T/Vua, Ei, Bii.

Misien) (V9M, Gryaznov, V, S.

Sm i rnov, L, to I vanova, Δ.

P, hii r; chenko), Doklac!y ANSSSR
), 1970. vol, 190. p.

Using a membrane catalyst formed as a foil from an alloy consisting of 94.2% by weight balanoum and 5.8% by weight nickel, prepared according to the prior art method described in the publication No. 144, 91. did.

The catalytic properties of this membrane catalyst were investigated by hydrogenating 1°3-pentanoene in a reactor partitioned into two chambers by the catalyst. supplying hydrogen into one chamber at a rate of 30 or 75 d/min;
In the other chamber, 1,3-pentanoene vapor was fed into the argon flow at a rate of 10 d/min under a hydrocarbon vapor pressure of 10 mHg. The composition of the r-catalytic reaction products produced at various temperatures of the hydrogenation process is shown in Table tIS7 below.

17! Pentane 1-pen 2-ben 1,3-pentatene
Ten Dien 30 100 1.0 13,0 36,0
50,0150 1.9 23.3 49.
7 25,175 100 1.0 15,
0 26,0 58,0150 1.3 1
? , 5 60,0 21.2 No. 4.5. From the data presented in Tables G and 7, it can be seen that the r! , Sakucle
pth) is significantly higher than with decatalysts produced by prior art methods, which makes it possible to increase the loading per unit surface area of the reaction surface of the catalyst and increase the hydrogenation process. I understand.

Example 15 A study of the catalytic properties of the decatalyst prepared as a foil according to Example 1 above was carried out by hydrogenating cyclopentanoene in a reactor partitioned into two chambers by the decatalyst. Hydrogen was fed into one chamber at a rate of 75 d/min, and cyclopentadiene vapor was fed into the other chamber at a rate of 60-7 min under a hydrocarbon vapor pressure of 180 mF with an argon flow. Supplied inside.

Table 8 shows the composition of the catalytic reaction products obtained at various temperatures of the hydrogenation step.

Table 8 Cyclopentane Cyclopentene Cyclopentadiene 40 8.0 92.0
-60 14.2 85.8
-100 53.4 46.1
0.5150 55.1 40.2
4.7200 16.3
62,3 21. At temperatures in the range of 440 to 60°C, cyclopentadiene is sufficiently hydrogenated to mainly form cyclopentene, which is the starting monomer for the production of synthetic rubber.

Example 16 Using 25% nitric acid aqueous solution to remove mercury, Example 8
The study of the catalytic properties of the decatalyst prepared according to the method was carried out by hydrogenation of 1-pentene in a reactor partitioned into two chambers by the above catalyst. Hydrogen is supplied into one chamber at a rate of 100 wILZ, and 1-pentene vapor is supplied into the other chamber at 400 wILZ.
The feed was carried out in a stream of argon at a rate of 50-7 minutes under a hydrocarbon vapor pressure of .

The composition of the catalytic reaction products obtained at various temperatures of the hydrogenation process is shown in the ttss table.

tjS9 Table pentane 2-pentene 1-pentene 20
99.8 0,240
97.0 2.1 0.960
90.1 7.2 2.7100
B5,4 11.5 3.1
150 55.7 29.4 14
．． 9 As is clear from Examples 12.13.14 and 16 above, the hydrogenation of unsaturated hydrocarbons by the decatalyst of the present invention within the temperature range of 20 to 100°C proceeds substantially completely; (Allowing the sl preparation of the desired product without the need for further separation from the initial reagents.

Therefore, the decatalyst of the present invention can be applied over a wide temperature range (20
~200 °C), high softening rate of the starting hydrocarbon (100 °C)
%) and with high selectivity, it becomes possible to carry out the hydrogenation process of hydrocarbons to obtain products that constitute valuable raw materials in the production of synthetic rubber.

The method for producing a hydrogenation catalyst of the present invention makes it possible to obtain a decatalyst that selectively permeates hydrogen and has no through holes, and thus uses highly active elemental water leakage to achieve high selectivity and high It becomes possible to hydrogenate unsaturated hydrocarbons at a high conversion rate.

By using the method according to the invention, a common crystal vt
A decatalyst having a porous layer and a non-porous layer with a structure of Resistance is ensured.

Claims (2)

[Claims] (1) A membrane made from an alloy of 80 to 95% by mass of palladium and 5 to 20% by mass of ruthenium or rhodium and consisting of a nonporous layer and a porous layer disposed on one or both sides of the nonporous layer. , the area of the porous surface is 150 to 820 cm^2 of pores per cm^2 of the membrane surface, and the thickness ratio of the porous layer to the non-porous layer is 1:5, respectively.
1,000. A palladium-based catalyst for the hydrogenation of unsaturated hydrocarbons with hydrogen. (2) depositing a catalytically inactive metal on a catalytically active metal, maintaining these metals at a temperature that ensures their interdiffusion, and then separating the catalytically inactive metal from the catalytically active metal; A method for producing a catalyst according to claim 1 by chemically removing metals, the catalytically active metals being 80-95% by weight of palladium and 5-20% by weight of ruthenium. or as a membrane of an alloy consisting of rhodium, copper or mercury as a catalytically inactive metal at a thickness ratio of 1:10 to 100 of the catalytically inert metal to the membrane, on one or both sides of the membrane. When copper is used as a catalytically inert metal, the film on which copper is deposited is heated at 300 to 800°C.
If mercury is used as the catalytically inactive metal, the membrane on which mercury is precipitated must be maintained at a temperature of -10 to 1.
Maintain a temperature of 50 °C and chemically remove mercury from the membrane using a 40-60% iron(III) chloride aqueous solution or a 20-30% iron(III) chloride solution.
% nitric acid aqueous solution.