FR2595092A1 - CATALYST FOR HYDROGENATION BY HYDROGEN OF UNSATURATED HYDROCARBONS AND METHOD FOR PREPARING THE SAME - Google Patents

Abstract

THE CATALYST FOR HYDROGENATION WITH HYDROGENES OF NON-SATURATED HYDROCARBONS IS A MEMBRANE MADE OF PALLADIUM MASS 80-95 MASS AND 5-20 MASS OF RUTHENIUM OR RHODIUM AND COMPOSED OF A NON-POROUS LAYER AND A POROUS LAYER DISPOSED ON ONE OR THE BOTH SIDES OF THE FIRST LAYER; THE POROUS SURFACE HAS 150-820 CM OF PORES AT THE CM OF THE SURFACE OF THE MEMBRANE, THE RATIO OF THE THICKNESS OF THE POROUS LAYER TO THE THICKNESS OF THE NON-POROUS LAYER BEING 1 (5-1000), RESPECTIVELY. THE PROCESS FOR PREPARING THE CATALYST CONSISTS OF APPLYING TO THE SURFACE OF THE MEMBRANE MADE OF ALLOY SUSENDED ON ONE OR ON TWO SIDES OF COPPER OR MERCURY, ABANDONING THE MEMBRANE WITH COPPER APPLIED ON AT 300-800 C, AND WITH MERCURY APPLIED TO A TEMPERATURE OF -10 TO 150 C, AND TO ACHIEVE THE CHEMICAL EXTRACTION OF COPPER OR MERCURY.

Description

The present invention relates to the technology

  catalyst preparation and, in particular, to obtain

  a catalyst for the hydrogen hydrogenation of unsaturated hydrocarbons, especially olefins

  and dienes, and its method of preparation.

  Metallic catalysts with a highly developed surface are already known which are in the form of porous carrier granules (alumina,

  silica gel, coal) on the surface of which is applied

  as an active metal catalyst. We also use

  metal catalysts with highly

  veloped (Raney nickel catalysts) (C. N. Setterfield "Heterogeneous Catalysis in Practice, Mc

Graw Hill Inc., New York, 1980).

  The known processes of preparation of the said

  Highly developed surface metal catalysts consist in applying to a granulated support a metal active in catalysis in a form

  highly dispersed. In addition, catalytic

  Highly developed surface metal catalysts (Raney nickel catalysts, for example by leaching certain active catalytic metal alloys)

  and aluminum, silicon, etc. (see the indi-

above).

  The catalysts mentioned do not exhibit selective permeability to hydrogen. They are not mechanically resistant which leads to

  wear through attrition during their use.

  It is not possible to manufacture membranes with

of these.

  Surface membrane catalyst is known

  highly developed in the form of a min-

  this or a tube on the surface of which is black palladium or another metal. The sheet or tube made of palladium or its alloy is made of silver or nickel (see M. Gryaznov, V. Smirnov, K. Ivanova, A. Mischenko, Doklady Akademi nauk SSSR - Proceedings of the Academy of

  U.S.S., 1970, Vol. 190, p. 144).

  The process for preparing such a catalyst

  It consists in applying to the surface of a membrane made in the form of a thin sheet or of a palladium alloy tube, for example with silver, by a chemical or electrochemical route, a layer of palladium black. or another metal active in catalysis, in particular nickel (cf.

  source indicated in the above).

  However, the known method does not guarantee the obtaining of a solid coating on the palladium black or other metal membrane. In addition, the

  implementation of another active metal in the catalyst

  1 c often leads to a decrease in the hydrogen per-

  membrane catalyst since a large proportion of

  tion of the palladium alloy membrane surface becomes inaccessible to the molecules of hydrogen and the organic substance. In case of prolonged work in a medium of hydrogen, air and hydrocarbons

  the black layer disintegrates and separates.

  On the other hand, a catalyst is known for the hydrogen hydrogenation of nonhydrocarbons.

  saturated which is in the form of a

  alised into a metal building material at the

  surface of which is disposed a porous layer of

  Catalyst active in catalysis, for example nickel, palladium or platinum (see US International Patent No. 218,830, International Patent Classification, BOI J 25/00, published in the Bulletin).

  inventions of U.S.S., No. 24, 1967).

  The process for preparing said catalyst consists in applying to the surface of the support a layer of active metal in the catalysis which is

  covers with an inactive metal layer in the cata-

  lysis, such as aluminum or zinc, to be abandoned

  at a temperature of 300 - 10000C for the diffusion

  mutual conversion of the active and the inactive metal in

  catlyse, which is then extracted chemically

  of aluminum or zinc from the active metal

  in the catlyse by leaching with the hydrate of o-

  sodium hydroxide or potassium hydroxide. The thick-

  of the inactive metal layer in the catalysis is equal to the thickness of the active metal layer

  ten times over (see the indi-

in the above).

  This method does not make it possible to obtain a

  membrane lyser on which the hydrogenation processes

  would take place with the implementation of the hy-

  active (atomic) drug diffusing through the

  brane. On the catalyst prepared by the indi-

  that the reactions take place using molecular hydrogen in the presence of a competitive adsorption of hydrogen and hydrocarbon

  unsaturated, which compromises the hydrogenation rate.

  tion and selectivity of the process.

  It was therefore proposed to create a catalyst

  porous highly developed surface but

  without open pores, offering selective permeability

  increased hydrogen strength and mechanical strength of the porous layer, as well as finding a process for preparing the catalyst having the

properties indicated.

  This is achieved with the catalyst according to the invention for the hydrogenation of palladium-based unsaturated hydrocarbons with hydrogen, it being understood that, according to the invention, said catalyst is a membrane made of an 80-95% alloy.

  mass of palladium and 5-20% by mass of

  rhodium or rhodium and having a non-

  porous layer and a porous layer arranged on a single

  on either side of the first layer,

  it being understood that the porous surface comprises 150-

  820 cm2 of pores per square centimeter of the surface of the membrane and that the ratio of the thickness of the porous layer to the thickness of the non-porous layer

is 1 / (5-1000) respectively.

  The invention also relates to a process for preparing said catalyst by applying an inactive metal in the catalysis of the active metal in

  catalysis, with the abandonment of said metals at a temperature of

  erated by their mutual diffusion,

  and subsequent chemical extraction of catalytic metal

  inactive from the active metal in the cat-

  lysis, it being understood, according to the invention, that the active metal is used in catalysis in the form of

  a membrane made of an alloy composed of 80-95% mas-

  palladium and 5-20% by mass of ruthenium

  nium or rhodium, that as inactive metal in catalysis copper or mercury is used and applied to the surface of the membrane of a single

  listed on either side for a report of the

  thickness of the inactive metal layer in the catalyst

  to the thickness of the membrane of 1 / (10-100), being

  heard that, if used, as an inactive metal

  in catalysis, copper is

  do not with the copper deposited on a temperature of 300-800 C, and one carries out the extraction of the copper

  of the membrane by treating said membrane with

  trichloroacetic; when used as an inactive metal in the catalysis of mercury, it is abandoned

  the membrane with the mercury deposited on it at a temperature

  between -10 and 1500C and the chemical extraction of mercury from the membrane

  by treating the membrane with an aqueous solution at 40-

  % iron (III) chloride or solution

  20-30% aqueous nitric acid.

  The claimed process makes it possible to obtain a

  membrane catalyst without open pores, having a

  highly developed porous surface (up to 800 cm2 of pore area per square centimeter of surface

  of the membrane) which increases the productivity of the

  a catalyst in the hydrogenation of non-hydrocarbons

  saturated thanks to the use of atomic hydrogen

  than. Selective permeability to hydrogen increases

  you substantially. Thus, at room temperature

  biante (18-25 C). The diffusion of hydrogen through

  to a membrane catalyst prepared by the claimed process is 5 to 10 times higher than that

  through the known membrane catalyst, which allows

  put into operation the catalyst membrane prepa-

  by the method of the invention for carrying out the hy-

  hydrogenation of non-hydrocarbon hydrocarbons

  at low temperatures (20-40 C). In addition, the catalyst obtained by the process according to the invention

  is characterized by increased mechanical resistance

  of the porous layer which does not decay at

  during the exploitation and regeneration of the

membrane talyseur.

  As stated in what precedes

  yielded, as active metal in the catalysis, an alloy composed of 80-95% by mass of palladium and 5-20% by mass of ruthenium or

  rhodium. It is not advantageous to use an alli-

  less than 80% by mass in palladium

  dium because the diffusion of hydrogen through

  alloys of this kind is very low, whereas in pre-

  If the palladium content exceeds 95% by mass, the alloys become unstable in a hydrogen atmosphere and easily undergo

disintegration.

  Reduction (decrease) in size

  of the porous surface of the membrane catalyst above

  under 150 cm2 of pores to the square centimeter of the

  Membrane surface is not recommended because the

  The effectiveness of such a membrane catalyst is insufficient.

  For a porous surface size greater than 820 cm 2 of pores per square centimeter of the surface of

  membrane, the porous layer begins - crumbling.

  The increase in the ratio of the thickness of

  the porous layer to the thickness of the non-porous layer

  to a value greater than 1/5 results in a

  reduction of the mechanical strength of the catalyst

  brane. Decreasing the thickness ratio to less than 1/1000 is not advantageous because the activity of such a catalyst would be low. It is not advantageous to take a thick report

  of the inactive metal layer from the catalytic point of view

  than at membrane thickness greater than 1/10 because a higher amount of inactive metal in the catalysis would result in the formation of pores passing through the

  membrane. A thickness ratio of less than 1/100

  has insufficient spongiosity of the surface of the membrane, which does not allow to obtain a catalyst

highly active hydrogenation.

  It is not recommended to raise above

  800 C the temperature at which the membrane is dropped

  do not copper layer. Indeed, at higher temperatures

  there would be a deeper diffusion of the

  in the superficial layer of palladium alloy

  dium, which in the course of subsequent treatment by the

  Trichloroacetic acid would not completely eliminate copper which adversely affects the activity of the membrane catalyst. Below 3000C, the diffusion of copper within the palladium alloy

  is strongly inhibited, and during the dissolution of the

  With acid, no porous layer is formed.

  The temperature at which the membrane with the mercury layer is abandoned, is limited between 10 and 150 C for the same reasons as in the

  case of the membrane with the copper layer.

  To dissolve the copper which has penetrated by diffusion within the membrane, it implements trichloroacetic acid, this solvent, by reacting with the copper does not react with the active metals in catalysis such as palladium, ruthenium and

  the rhodiufn, which makes it possible to obtain a po-

  reuse of the surface of the membrane catalyst.

  Nitric acid with a lower concentration

  at 20% dissolves the mercury badly, and for this reason

  dilute solutions of nitric acid are not advan-

  to dissolve mercury while

  nitric acid concentrations higher than 30% it is palladium that begins to dissolve as well

  that ruthenium and rhodium enter the

  position of the membrane catalyst. Analogous arguments

  This concerns the choice of the concentration of

  aqueous solution of iron (III) chloride.

  The membrane catalyst for the hydrogenation is in the form of a sheet, a plate or a tube. Said membrane is made of palladium - ruthenium or palladium - rhodium alloy. She is

  composed of a non-porous layer and a porous

  that is, the porous layer can be disposed either on either side of the non-porous layer or on one side of said layer. In the latter case,

  performs the hydrogenation on the side of the porous layer.

  The ratio of the thickness of the porous layer to the

  thickness of the non-porous layer is 1 / 5-1000,

  2- pectively. The size of the porous surface is -820 cm 2 of pores per square centimeter of surface

membrane catalyst.

  The membrane catalyst claimed according to the invention is prepared in the following manner. First,

  it is applied to the clean surface of the membrane

  felt, for example, in the form of a sheet, a plate or a tube, made of a palladium-ruthenium or palladium-rhodium alloy, on one or

  on both sides a thin layer of copper or

  cure with a ratio of the thickness of the layer of

  inactive metal in catalysis at the thickness of the mem-

  brane 1/10 to 1/100. It is possible to apply the copper on the membrane by vacuum evaporation, by

  an electrochemical or diffusion welding process

  cold welding; it is advantageous to apply the copper to the membrane by dipping or by a method

  casting. The membrane is abandoned with the layer

  plied with copper or mercury at a temperature

  completed (300-800 C in the case of copper, minus 10-

   C, in the case of mercury) and then placed in a suitable solvent. For copper, we take trichloroacetic acid and in the case of mercury, a 40-60% aqueous solution of iron chloride

  (III) or a 20-30% aqueous solution of nitric acid

  than. After drying, a catalyst is obtained

brane with porous layer.

  The membrane catalyst prepared in the manner described with regard to its permeability is tested.

  to hydrogen by the dynamic process (by

  with the use of a katharometer,

heat conductivity).

  To carry out the hydrogenation of hydrocarbons

  In the case of unsaturated bonds, eg, 1,3-pentadiene, pentene, cyclopentadiene, the membrane catalyst is placed in the reactor so that it partitions the inner cavity of the reactor into two chambers. In one of the chambers, one places hydrogen and in the other the substance to be hydrogenated. Hydrogen diffuses through the membrane catalyst into the other chamber in the active atomic form and reacts with the substance to be hydrogenated on the porous surface of the

  membrane catalyst with formation of the final product.

  The composition of the product of the catalysis is determined

  born by chromatography. The thickness of the porous layer and the non-porous layer are determined using

of a microscope.

  Other features and advantages of the present invention will be better understood when reading

  of the following description of several examples

of its concrete realization.

EXAMPLE 1

  We degrease a thin sheet of a thickness

  of 100 μm in alloy composed of 90.2% by weight of

  ladium and 9.8% by weight of ruthenium, washed with distilled water and applied to the surface of said sheet on both sides by vacuum evaporation

  copper layers with a thickness of 2 μm each.

  The sheet is carried with the copper layers deposited on it at a temperature of 800 C, after which

  it is left at the above temperature for 3 hours.

  Then, the thin sheet is cooled, placed in trichloroacetic acid and left there until the complete extraction of the copper. A membrane catalyst is obtained in the form of a thin sheet made of the aforesaid alloy and composed of a non-porous layer with a thickness of 95 μm and porous layers.

  surface areas on either side of the

  che porous and having a thickness of 2 Fm each.

  The size of the porous surface measured by the method

  BET (Drrunauer S., Emmett P.H., Teller E.) equals 820 cm 2 of pores per square centimeter of the surface of

the membrane.

  The permeabilities (J) to the hydrogen of the

  Membrane catalyst prepared as described above and the initial sheet (untreated) are given in Table I.

TABLE I

Temperature, OC 200 300 350 400

( at

  (- (Coefficient of permeability to hydrogen of the catalsyeur (membrane, J.104, 4.42, 10.2, 14.2, 16.6 (cm2, s-1.Pa-O, 5 () -, ( Coefficient of Permeability at) (Hydrogen of Sheet Y (initial thin, J.104, 2.14, 5.1, 6.8, 8.95) cm2 sl.MPa-05) ()

  As the data cited above show,

  meability of the membrane to hydrogen after its treatment

increased double.

EXAMPLE 2

  It is applied to an alloy thin sheet

  composed of 80% by mass of palladium and 20% by mass

  rhodium thickness of 50 μm, as de-

  In Example 1, copper layers of a thickness

  0.5 pm each. We wear the thin sheet with

  the layers of copper deposited on it at a temperature of

  300 C and maintained at the above-mentioned temperature

  te for 3 hours. Then, the copper is extracted from

  the membrane by dissolving it in trichloroacid

  acetic. A membrane catalyst analogous to

  the one described in Example 1, with a thickness of

  porous 0.2 μm layer for a thickness of

  porous layer of 49 pim. The size of the surface area

  The membrane catalyst is 410 cm 2 of pores per square centimeter of the surface of the membrane. The coefficient of hydrogen permeability of the membrane catalyst at a temperature of 350 ° C. is 15.1. 10-4 cm2.s-l.MPa-O5

EXAMPLE 3

  It is applied to the outer surface of a tu-

  be having an outer diameter of 1.2 mm, a thick

  100 pum wall, made of alloy of the same composition as in Example 1 a layer of copper

  1 pum thick. We abandon the tube with the

  copper foil deposited at a temperature of 550 ° C

  for 2 hours. After extraction of the copper with trichloroacetic acid, a membrane catalyst is obtained in the form of a tube whose wall is made of the aforesaid alloy and consists of a non-porous inner layer with a thickness of 99 μm. and a layer

  porous exterior with a thickness of 1> m.

  The size of the porous surface of the catalyst

  Its membrane is 620 cm 2 of pores per square centimeter of the membrane surface. The coefficient of permeability to hydrogen at a temperature of 350 ° C.

is 7.5 × 10 -4 cm 2 .s -1-MPa-0.5.

* EXAMPLE 4

  A thin sheet of thick

  100 pum alloy consisting of 90.2% by weight of palladium and 9.8% by mass of ruthenium a thin sheet of copper with a thickness of 5 μm and

  compresses it under a pressure of 0.2 MPa at a temperature of

  300 C for 10 hours. There is a

  diffusion by the two metals. After cooling

  of the bimetallic thin film, the

  copper by dissolving it in trichloroacetic acid.

  A membrane catalyst is obtained in the form of a thin sheet made of the aforesaid alloy and composed of a non-porous layer with a thickness of 98 μm and

  a porous layer with a thickness of 2 .mu.m. The big

  The porous surface of the membrane catalyst is 740 cm 2 of pores per square centimeter of the surface.

  of the membrane. The coefficient of permeability of the cat-

  The hydrogen-lysing agent at a temperature of 200 ° C. is 7.10 -4 cm.sup.2.sup.-1 .MPaO.sub.5 and at a temperature of 300.degree.

from 11.0 × 10 -4 cm.sup.-1 .MPa-0.5.

EXAMPLE 5

  On both sides of a 100 μm thick foil made of an alloy composed of 2% by weight of palladium and 9.8% by weight of ruthenium, the method is applied by dipping.

  layers of mercury with a unit thickness of 4 "m.

  We leave the thin sheet with the layers of sea-

  cured on it at a temperature of 60 C

  5 hours after which it is placed in a 60% aqueous solution of iron (III) chloride,

  it is kept there until the sea is completely dissolved.

  cure and washed with distilled water until the absence of the reaction to the chlorine ion. After a treatment of this kind, a membrane catalyst is obtained in the form of a thin sheet made of the aforesaid alloy and composed of a non-porous layer of a thickness

  of 92 μm and porous superficial layers

  on either side of the non-porous layer and having a thickness of 4 μm each. The size of the porous surface of the membrane catalyst is 520

  cm2 of pores to the square centimeter of the mem-

brane.

  The following Table 2 shows the data

  lative to the hydrogen permeability of the catalyst

  membrane obtained according to Example 5.

d e.t M-;

TABLE 2

  T Temperature, OC 200 300 350 400 () (Coefficient of permeability (with hydrogen, J.104 4.2 9.1 12.4 14.7 <cm2 sl.MPa-0.5 ()

EXAMPLE 6

  It is applied to a plate with a thickness of

  1000 μm alloy composed of 92% by weight palladium

  dium and 8% by weight of rhodium as described in

  Example 5 Mercury layers of a uniform thickness

  5 pm. The plate is left with the mercury layers placed on it at a temperature of minus 10 ° C. for 3 days. Then, the mercury is extracted from the plate by treating with a 40% aqueous solution of iron (III) chloride brought to the boil. We obtain

  a membrane catalyst in the form of a plate

  alloy alloy and comprising a non-coated layer

  999 pum thick and superficial layers

  porous surfaces arranged on either side of the

  not porous and having a thickness of 0.5 pm each.

  The size of the surface of the membrane catalyst is cm 2 of pores per square centimeter of the surface of the membrane, while its coefficient of permeability to

  the hydrogen at a temperature of 350 ° C. is equal to 12.9.

-4 cm2.s-1 .MPa-0.5.

EXAMPLE 7

  A thin sheet of 100 μm thickness made of an alloy of 94% by mass of palladium and 6% by mass of ruthenium is applied on both sides of the layers of mercury, 8 μm thick.

  each by proceeding by the method of casting. We abandon

  gives the thin sheet with the layers of mercury

  The mercury is extracted by treating the membrane with a 50% aqueous solution of iron (III) chloride. A membrane catalyst is obtained under

  - 05 in the form of a thin sheet made of sus-

  said and composed of a non-porous layer of thick

  98 μm and porous surface layers disposed on either side of the non-porous layer and each having a thickness of 1) m. The size of the porous surface of the membrane catalyst is 280 cm 2 of pores per square centimeter of the

  membrane; its coefficient of permeability to hydro-

  gene at 350QC is equal to 14.1.10-4 cm2.s-l.MPa-O'5

EXAMPLE 8

  An alloy membrane catalyst is prepared

  95% by mass of palladium and 5% by weight

  rhodium as in Example 7, but

  mercury by placing the thin sheet after a

  temperature at 150 ° C in an aqueous solution of

  nitrate of various concentrations.

  The thickness of the non-porous layer and the porous layer, the size of the porous surface and the hydrogen permeability (at the temperature of 350 ° C.) of the membrane catalyst according to the concentration of the nitric acid used are indicated in the

Table 3.

TABLE 3

  (Concentration of the solution (aqueous nitric acid,%) (Thickness of each layer (porous, im 2 3.5 5 (Thickness of the non-porous layer, pm 85 70 50

(Size of the surface area

  (reuse, cm2 of pores / cm2 310 450 480

2595092 -

  TABLE 3 (Continued) () (Coefficient of Permeability) (Hydrogen J.104) ((cm2 s-l.MPa-0.5) 12.6 14.8 13.2)

(.)

EXAMPLE 9

  On either side of a 900 μm thick plate made of alloy of the same composition as in Example 1, mercury layers 5 μm thick were applied to the quench. We give up

  the plate at a temperature of 10 C for a day.

  Then, the plate is placed in an aqueous 20% nitric acid solution for 1 hour. We get a

  membrane catalyst in the form of a plate

  alloy and comprising a non-porous layer with a thickness of 90 μm and layers

  surface areas on either side of the

  non-porous cheese with a thickness of 0.45 μm each.

  The size of the porous surface is 250 cm 2 of pores per square centimeter of the surface of the

  membrane catalyst while its coefficient of perm

  mecanicity with hydrogen at 350 C equals 13.4.10-4 cm2.S-1 .MPa-O, 5

EXAMPLE 10

  On both sides is applied a thin sheet of 100 μm thick made of

  same composition as in Example 1 of the sea

  cure of a unit thickness of 10 pm. We leave the sheet with the layers applied on it to a

  temperature of 145 C for 1 hour. After cooling

  the thin sheet is placed in a solution

  60% iron (III) chloride and is

  boils. A membrane catalyst is obtained

  not in the form of a thin sheet made in alloy

  above mentioned and composed of a non-porous layer of 96 μm

  of thickness and porous surface layers

  placed on either side of the non-porous layer and having a thickness of 2 Hum each. The size of

  the porous surface is 540 cm 2 of pores

  square meter of the surface of the membrane catalyst while its coefficient of permeability to hydrogen at 300 C is equal to 7.9.10-4 cm2. s-1.MPa-0.5 and at 400 ° C,

13.2.10-4 cm2.s-.MPa-0.5.

  As the examples cited show, the

  hydrogen permeability of the membrane catalyst

  significantly (1.5 to 2 times) compared to the hydrogen permeability of the initial thin sheet. This makes it possible to increase the productivity of the membrane catalyst in the hydrogenation reaction

unsaturated hydrocarbons.

  Examples are:

  11 to 16 for carrying out the hydrogenation of hydro-

  unsaturated carbides on the membrane catalyst

  diket prepared according to Examples 1, 2, 3, 5, 8 and a known membrane catalyst prepared according to the process described in the publication: V. Gryaznov M., S. Smirnov S., Ivanova L. L, A. Mischenko P. Doklady

  Akademii nauk SSSR, 1970, Vol. 190, p. 144.

EXAMPLE 11

  The catalytic properties are studied

  membrane catalyst prepared according to the Exemile

  3 and having the shape of a tube by hydrogenating penta

  1,3-diene in a reactor divided into two chambers by said membrane catalyst. In one of the chambers formed by the tube cavity, hydrogen is admitted at a rate of 30 ml / min, in the other chamber formed

  by the inner wall of the reactor and the outer wall

  pipe is allowed a mixture of pentadiene-1,3 with argon at a rate of 10 ml / min and a pressure of pentadien-1,3 vapor equals 10

Torr. (1330 Pa).

  Table 4 shows the composition of the pro-

  the result of catalysis obtained at various temperatures

of the hydrogenation process.

TABLE 4

  (Tempera- tion of the product of the catalysis, (ture, C% mol

  (_____________________ _________) ______

  (pentane pentene-1pentene-2 pentadiene-1,3

63.0 - 1.1 35.9

(100 77.9 0.1 12.0 10.0

82.5 1.3 2.2 14.0

()

EXAMPLE 12

  The study of the catalytic characteristics of the membrane catalyst prepared according to Example 5 in the form of a thin sheet is carried out by hydrogenation of pentadiene-1,3 in a reactor divided into two chambers by said catalyst. In one of the chambers, a stream of hydrogen is sent at a speed of 30

  ml / min and in the other chamber the vapors of pentadiene

  ne-1,3 in a flow of argon at a rate of 75 ml / min at a vapor pressure of the Torr hydrocarbon (2 KPa);

  Table 5 shows the composition of the pro-

  the result of catalysis obtained at various temperatures

execution of the hydrogenation. -

TABLE 5

  (Tipra- composition of the product of catalysis, (ture, C% mol)

(__)

  pentene pentene-1 pentene-2.)) (100.11.3 15.9 72.8)

1OO 11.3 15.9 72.8)

)

13.1 16.8 70.1

20.9 6.4 72.7

20.9 6.4 72.7)

)

EXAMPLE 13

  The catalytic characteristics of the membrane catalyst prepared according to Example 2 in the form of a thin film by hydrogenating the

  1,3-pentadiene in a reactor divided into two chambers

  by said catalyst. In one of the chambers hydrogen is admitted at a rate of 30 ml / min and in the other chamber the vapors of pentadiene-1,3 in a stream of argon at a rate of 30 ml / min. a vapor pressure of the hydrocarbon of

Torr. (2 KPa).

  Table 6 shows the composition of the pro-

  the result of the catalysis obtained as a result of hydro-

  generation at various temperatures.

  EXAMPLE 14 (control) A membrane catalyst is used in the form of an alloy thin film composed of 94.2% by weight of palladium and 5, 8% by weight of nickel

  prepared according to a known method described in the

  Mr. V. Gryaznov, Mr. S. Smirnov, Mr. L. Ivanova, Mr. A. Mischenko. Doklady Akademi nauk. SSSR, 1970,

flight. 190, p. 144.

TABLE 6

  (Composition of the product of the catalysis, (ture, C% mol)

(3

(pentane pentene-1 pentene-2) ()

(100 14.9 9.6 75.5)

(

32.0 4.0 64.0

(150 25.0 5.4 69.6)

  () The study of the catalytic characteristics of said membrane catalyst is carried out by hydrogenation of pentadiene-1,3 in a reactor divided into two chambers by said catalyst. In one of the chambers, hydrogen is admitted at a rate of 30 or 75 ml / min and in the other chamber

  1,3-pentadiene in an argon flow at one

  10 ml / min and under a pressure of 10 Torr hydrocarbon vapors. (1330 Pa). In Table 7, the composition of the product of the

  catalysis obtained under varying temperatures of

  hydrogenation and at various speeds

hydrogen intake.

TABLE 7

  (Rate of Ad- Tempera- Composition of the product of the catalysis, (mission of ture, C% mol

(hydrogen -

  (ml / min pentane pentene-1 pentene-2 pentadiene-1,3) ()

(30 100 1.0 13.0 36.0 50.0)

1.9 23.3 49.7 25.1

()

100 1.0 15.0 26.0 58.0

1.3 17.5 60.0 21.2

  Starting from the data cited in

  4, 5, 6 and 7, we can see that the hydrogen

  the membrane catalyst prepared according to the claimed process is substantially higher than the membrane catalyst prepared by the known process, thereby increasing the charge per unit

  reaction surface area of the catalyst and

proud hydrogenation.

EXAMPLE 15

  The study of the characteristic characteristics of

  talytic membrane catalyst prepared following

  Example 1 in the form of a thin sheet of

  cyclopentadiene in a reactor

  ge in two chambers on the catalytic membrane indi-

  than. In one of the chambers, hydrogen is admitted at a rate of 75 ml / min and in the other chamber

  cyclopentadiene vapors in a stream of

  at a speed of 60 ml / min under a pressure of

  hydrocarbon vapors of 180 Torr. (24 KPa).

  Table 8 gives the composition of the product of the catalysis obtained at temperatures

  various embodiments of the hydrogenation.

TABLE 8

  (Composition of the product of catalysis, ((ture, C% mol to) cyclopentane cyclopentene cyclopentadiene) ()

(40 8.0 92.0 -)

14.2 85.8 -

53.4 46.1 0.5)

(150 55.1 40.2 4.7

(200 16.3 62.3 21.4)

  At a temperature of 40-60 ° C, the cyclopentane

  tadiene is hydrogenated thoroughly, and it is then formed

  preferably cyclopentene which is a monomer of

  part for the preparation of synthetic gums.

O5

EXAMPLE 16

  The study of the characteristic characteristics of

  of the membrane catalyst prepared according to Example 8 with the implementation for the extraction

  mercury from a 25% aqueous solution of nitric acid

  by hydrogenating pentene-1 in a reactor divided into two chambers by said catalyst. In

  one of the chambers one admits hydrogen to a

  100 ml / min and in the other, pentene-1 vapors in a stream of argon at a rate of 50 ml / min under a hydrocarbon vapor tension

400 Torr. (53 KPa).

  Table 9 shows the composition of the pro-

  the result of catalysis obtained under varying temperatures.

  performance of the hydrogenation.

TABELAU 9

  (Composition of the product of the catalysis, (ture, C% mol (pentane pentene-2 pentene-1 (to ()

(20 99.8 - 0.2)

40 97.0 2.1 0.9

(,)

(60 90.1 7.2 2.7)

85.4 11.5 3.1

(,)

(150 55.7 29.4 14.9)

  () As shown in examples 12, 13, 16, the hydrogenation of unsaturated hydrocarbons on a membrane catalyst according to the invention. in a temperature range of 20 to 100oC, is practically 100%, which makes it possible to obtain

  covered products that do not require their separation from

departure time.

  Thus, the membrane catalyst according to the invention

  vention allows the hydrogenation of hydro-

  carbides in a wide temperature range (from 20 to 2000C) with a high conversion rate (up to%) of the starting hydrocarbons, in a more

  selective, with products that are

  value for the production of rubber

synthetic bucks.

  The claimed process for the preparation of

  hydrogenation catalyst makes it possible to prepare a catalyst

  selectively permeable membrane membrane with no through pores, which offers the possibility of hydrogenation with highly active atomic hydrogen

  unsaturated hydrocarbons with a conversion rate of

  high and with high selectivity.

  Thanks to the implementation of the

  diqué, a membrane catalyst having a

  crystalline structure common with the non-polar layer

  catalyst, which guarantees the mechanical strength of the porous layer and its stability during hydrogenation under hydrogen and hydrocarbons, and in case of regeneration by air.

Claims (2)

  1. Catalyst for hydrogenation with hydrogen   unsaturated hydrocarbon gene based on palladium,   characterized in that it consists of a membrane   made of 80-95% by weight of palladium alloy and   5-20% by weight of ruthenium or rhodium and   of a non-porous layer and a porous layer disposed on one or two sides with respect to   the first layer, it being understood that the surface area   reuse has 150-820 cm2 of pores per square centimeter   d of the membrane surface and that the ratio of the thickness of the porous layer to the thickness of the   non-porous layer is 1 / (5-1000) respectively.   2. Process for the preparation of a catalyst according to claim 1 by application of an inactive metal in the catalysis of a metal active in catalysis, by abandoning said metals at a temperature under which intervenes their mutual diffusion, and by subsequent chemical extraction. of the inactive metal in the catalysis out of the active metal in catalysis, characterized in that the active metal is used in the catalyst in the form of an alloy membrane composed of 80-95% by weight of palladium and 20% by weight of: ruthenium or rhodium, which in the case of inactive metal in catalysis is used copper or mercury and applied to the surface of the membrane on. one or both sides with a ratio of the thickness of the inactive metal layer in the membrane thickness catalysis of 1 / (10-100), provided that if it is used as an inactive metal in the copper is catalyzed, the membrane is left with the layer of copper deposited on it at a temperature of 300-8000C, and the copper is extracted chemically from the membrane by treatment of said membrane with trichloroacetic acid, and if   it is used as the inactive metal in the catalyst   mercury, the membrane is abandoned with the mercury   It is applied at a temperature between -10 and 150 ° C. and the mercury is extracted chemically from the membrane by treating the membrane with an aqueous 40-60% solution of iron (III) chloride or by aqueous solution of nitric acid to -30 %.