CN111097457B - Low-carbon alkane dehydrogenation catalyst and preparation method thereof - Google Patents

Low-carbon alkane dehydrogenation catalyst and preparation method thereof Download PDF

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CN111097457B
CN111097457B CN201811268935.2A CN201811268935A CN111097457B CN 111097457 B CN111097457 B CN 111097457B CN 201811268935 A CN201811268935 A CN 201811268935A CN 111097457 B CN111097457 B CN 111097457B
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CN111097457A (en
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刘昌呈
王春明
马爱增
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

A low-carbon alkane dehydrogenation catalyst comprises a spherical theta-alumina carrier and active components with the following contents calculated by taking the carrier as a reference:

Description

Low-carbon alkane dehydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, in particular to a low-carbon alkane dehydrogenation catalyst with active components distributed on the surface layer and a preparation method thereof.
Background
With the increase of crude oil processing amount in China, a large amount of low-carbon alkanes such as ethane, propane, isobutane and the like can be produced in the catalytic cracking process of an oil refinery. How to effectively utilize the resources and convert the resources into the low-carbon olefin with high added value has important significance for improving the economic benefit of the oil refinery.
Propylene is an important basic organic chemical raw material and is widely applied to the production of various chemical products such as polypropylene, acetone, acrylonitrile, propylene oxide, acrylic acid and the like; isobutylene is the primary feedstock for the production of Methyl Tertiary Butyl Ether (MTBE); the butylene is mainly used in the fuel fields of synthesizing useful gasoline components and synthesizing MTBE and ETBE gasoline additives by alkylation, superposition, isomerization and dimerization processes, and is widely applied to the chemical field. Therefore, the dehydrogenation of the low-carbon alkane to prepare the olefin is a feasible process route for producing the corresponding olefin by using the low-carbon alkane.
The supported platinum-based catalyst is an important type of low-carbon alkane dehydrogenation catalyst, and usually takes alumina as a carrier, and is modified by adding other components to improve the activity and selectivity of the catalyst. Because the dehydrogenation reaction of the low-carbon alkane is limited by thermodynamic equilibrium, the reaction is carried out under the harsh conditions of high temperature and low pressure. Too high reaction temperature can aggravate cracking reaction and deep dehydrogenation, accelerate the carbon deposition rate of the catalyst and inactivate the catalyst. Therefore, the development of a dehydrogenation catalyst with high activity, high stability and low carbon deposition rate becomes the key of the technology.
In order to reduce the carbon deposition rate of the catalyst, it is an effective method to modulate the distribution of the dehydrogenation active component, pt group metal, on the catalyst. US4786625, US4827072 and CN1018619B et al report that Pt group metals undergo surface impregnation by forming a chemical complex with an organic acid chelate, which complex is strongly attracted to a refractory oxide support, keeping the Pt group metals mainly on the outer surface of the support. The catalyst is suitable for dehydrogenation of C2-C30 alkane, especially long-chain alkane.
The catalyst of US5012027 contains, in addition to Pt, a second promoter selected from iridium, osmium, a third promoter selected from group IVA metals. And the concentration gradient of the second auxiliary agent metal is larger than that of the Pt group metal, and the second auxiliary agent is in eggshell type surface impregnation. The catalyst is also suitable for the dehydrogenation of alkanes containing 2 to 30 carbon atoms, in particular long-chain alkanes.
CN101612583B reports a long-chain alkane dehydrogenation catalyst with non-uniformly distributed active components, wherein platinum metal in the catalyst is mainly distributed on the surface of the catalyst as an active component, tin, alkali metal and VIII group metal selected from iron, cobalt, nickel and palladium are uniformly distributed in a carrier as an auxiliary agent, the carrier is gamma-alumina, and the catalyst is suitable for dehydrogenation reaction of long-chain alkane of C10-C15.
Disclosure of Invention
The invention aims to provide a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein the catalyst is used for preparing olefin by low-carbon alkane dehydrogenation, and has high activity and selectivity and low carbon deposit amount.
The low-carbon alkane dehydrogenation catalyst provided by the invention comprises a spherical theta-alumina carrier and active components with the following contents calculated by taking the carrier as a reference:
Figure BDA0001845553910000021
the average diameter of the spherical alumina carrier is 1.5-2.0 mm, the VIII group metal and the IA group metal are both distributed in a surface layer of which the thickness is 350-500 mu m from outside to inside of the spherical carrier, and the second metal component is uniformly distributed in the carrier and is selected from tin, germanium, lead, indium, gallium or thallium.
In the catalyst provided by the invention, the VIII group metal and the IA group metal are uniformly distributed in the surface layer of the spherical carrier with a certain thickness, the second metal component is uniformly distributed in the whole spherical carrier, and the catalyst is used for the reaction of preparing olefin by dehydrogenating low-carbon alkane, and has better reaction performance and lower carbon deposition amount.
Drawings
FIG. 1 is a radial distribution of platinum in catalyst pellets of the present invention.
FIG. 2 is a radial distribution plot of potassium in the catalyst pellets of the present invention.
FIG. 3 is a radial distribution of tin in the catalyst pellets of the present invention.
Detailed Description
The group VIII metal and the group IA metal in the catalyst provided by the invention are distributed in a surface layer with a certain thickness of a spherical carrier, the sphere center part basically does not contain the group VIII metal and the group IA metal, and the second metal component is uniformly distributed in the whole spherical carrier. The catalyst is used for the reaction of preparing olefin by dehydrogenating low-carbon alkane, and can greatly reduce the probability of dehydrogenation reaction of the low-carbon alkane in a sphere center area, thereby reducing the retention time of dehydrogenation product olefin in the catalyst, reducing the carbon deposition amount, and improving the conversion rate and the selectivity of the low-carbon alkane.
In the catalyst of the present invention, the group VIII metal content is preferably 0.1 to 1.0 mass%, the second metal component content is preferably 0.1 to 1.0 mass%, the group IA metal content is preferably 0.5 to 2.0 mass%, and the chlorine content is preferably 0.3 to 2.0 mass%.
In the catalyst of the invention, the group VIII metal is ruthenium, rhodium, palladium, platinum, iridium and osmium, preferably platinum, the second metal component is preferably tin, and the group IA metal is preferably potassium.
In the catalyst of the present invention, both the group VIII metal and the group IA metal are distributed in the surface layer of the spherical support having a thickness of 350 to 500. Mu.m, preferably 400 to 500. Mu.m, more preferably 420 to 500. Mu.m, from the outside inwards, and the core part is substantially free of the group VIII metal and the group IA metal, which means that at least 98 mass%, preferably at least 99 mass%, of the said components are distributed in the surface layer of the said thickness in the catalyst pellet.
The theta-alumina carrier has the following pore distribution: the pore volume of pores with the diameter of 2-10 nanometers accounts for 4-15 percent of the total pore volume, the pore volume of pores with the diameter of 10-20 nanometers accounts for 40-60 percent of the total pore volume, the pore volume of pores with the diameter of 20-50 nanometers accounts for 1.0-5.0 percent of the total pore volume, and the pore volume of macropores with the diameter of more than 50 nanometers but not more than 10 micrometers accounts for 20-50 percent of the total pore volume.
Preferably, the pore volume of pores with diameters of 2 to 10nm accounts for 7 to 15% of the total pore volume, the pore volume of pores with diameters of 10 to 20nm accounts for 43 to 60% of the total pore volume, the pore volume of pores with diameters of 20 to 50nm accounts for 1.0 to 5.0% of the total pore volume, and the pore volume of macropores with diameters of greater than 50nm but not greater than 10 μm accounts for 22 to 48% of the total pore volume.
The specific surface area of the theta-alumina carrier is 50-130 m 2 G, pore volume of 0.6-0.75 ml/g.
The preparation method of the low-carbon alkane dehydrogenation catalyst comprises the steps of impregnating a spherical theta-alumina carrier containing a second metal component with a mixed solution containing a VIII-group metal compound and a competitive adsorbent, wherein the competitive adsorbent is hydrogen chloride or a mixture of hydrogen chloride and chloroacetic acid, the mass ratio of the competitive adsorbent contained in the impregnating solution to the alumina carrier is 1.1-2.8%, the impregnating solution/solid ratio is 1.3-3.0 ml/g, drying and roasting the impregnated solid, impregnating with a solution containing an IA-group metal compound, drying, roasting and reducing, and when the competitive adsorbent is hydrogen chloride, the mass ratio of the hydrogen chloride contained in the impregnating solution to the alumina carrier is not more than 2.0%.
In the above method, when the theta-alumina carrier containing the second metal component is impregnated with the mixed solution containing the group VIII metal compound and the competitive adsorbent, the liquid/solid ratio of the impregnation is preferably 1.5 to 2.5ml/g.
When the competitive adsorbent is hydrogen chloride, the mass ratio of the competitive adsorbent to the alumina carrier contained in the impregnation liquid is 1.1 to 1.8%, preferably 1.2 to 1.8%.
When the competitive adsorbent is a mixture of hydrogen chloride and chloroacetic acid, the mass ratio of the hydrogen chloride to the alumina carrier in the impregnating solution is 0.2-0.8%, and the mass ratio of the chloroacetic acid to the alumina carrier is 1.2-2.0%. The said chloric acetic acid is dichloroacetic acid or trichloroacetic acid.
In the method, after the VIII group metal is introduced by impregnation, the obtained solid needs to be dried and roasted, and then the IA group metal is introduced by impregnation, and the liquid/solid ratio of the IA group metal introduced by impregnation is preferably 1.5-2.3 ml/g. The temperature for introducing the active component in each impregnation is preferably 20-70 ℃, the time is preferably 2-6 hours, the drying temperature of the solid obtained after impregnation is preferably 100-300 ℃, and the roasting temperature is preferably 450-630 ℃.
In the above method, when preparing the impregnation solution, the compound of the group VIII metal used is preferably chloroplatinic acid or ammonium chloroplatinate, and the compound of the group IA metal is preferably a hydroxide, nitrate or chloride of the group IA metal. The hydroxide of the group IA metal is preferably potassium hydroxide, the nitrate of the group IA metal is preferably potassium nitrate, and the chloride of the group IA metal is preferably potassium chloride.
In the above method, the second metal component in the theta-alumina carrier containing the second metal component may be introduced during the formation of the carrier or may be introduced by an impregnation method after the formation of the carrier.
In the above method, the carrier into which the group IA metal is introduced is impregnated, dried and calcined, and then reduced to reduce the group viii metal to the corresponding metallic state. The gas used for reduction is hydrogen or other reducing gas, and a mixed gas of hydrogen and inert gas can also be used. The reduction temperature is preferably 450 to 700 ℃, more preferably 500 to 650 ℃, and the reduction time is preferably 0.5 to 20 hours, more preferably 2 to 10 hours. The reduction may be carried out before the catalyst is charged into the reactor, or may be carried out after the catalyst is charged into the reactor before the dehydrogenation reaction.
In the method of the invention, the theta-Al 2 O 3 The preparation method comprises the following steps: firstly, roasting the formed alumina pellets at 450-650 ℃ to obtain gamma-Al 2 O 3 Then roasting at 900-1100 deg.C, preferably for 1-20 hr.
Preferably, the gamma-Al 2 O 3 Treating with 2-10 vol% air at 450-650 deg.c for 2-8 hr, and roasting at 900-1100 deg.c.
The aluminum oxide pellet is preferably formed by oil ammonia column or hot oil column, and the method for preparing the aluminum sol for the pellet can be that aluminum trichloride reacts with ammonia water at the temperature of 50-90 ℃, preferably 50-80 ℃, then the aluminum chloride is filtered and washed, acid solution is added into a filter cake to form the aluminum sol, or water is directly added into aluminum hydroxide powder to prepare slurry, and then acid is added into the slurry to prepare the aluminum sol. The acid used is preferably nitric acid or hydrochloric acid, to which organic acids, such as acetic acid, or citric acid, may also be added. If the alumina containing macropores is prepared, a proper amount of pore-expanding agents such as urea, kerosene, fatty alcohol-polyoxyethylene ether and the like are added into the alumina sol. And drying and roasting the wet balls obtained by drop ball forming to obtain the gamma-alumina balls.
And adding a compound containing a second metal component into the aluminum sol to obtain the theta-alumina carrier containing the second metal component.
If the second metal component is introduced by adopting an impregnation method, firstly, roasting the gamma-alumina prepared by roasting at 900-1100 ℃ to convert the crystal form of the alumina into a theta form, then, impregnating the theta form by using a compound solution containing the second metal component, drying and then, roasting at 500-630 ℃.
In the above method, the compound containing the second metal component used for introducing the second metal component into the theta-alumina support is preferably a tin-containing compound such as a chloride, bromide, nitrate, alkoxide or organic complex of tin, preferably stannous bromide, stannous chloride, stannic chloride pentahydrate, tetrabutyltin.
The catalyst provided by the invention is suitable for the reaction of preparing olefin by low-carbon alkane dehydrogenation. The low-carbon alkane reacts with the catalyst in the presence of hydrogen under the conditions of 400-800 ℃, preferably 550-650 ℃, and the pressure of 0.1-1.0 MPa, preferably 0.1-0.5 MPa (absolute pressure).
In the reaction process, the proper mass space velocity of the low-carbon alkane contacted with the catalyst is 0.1 to 20 hours -1 More preferably 0.5 to 10 hours -1 . The dehydrogenation reaction can also be carried out by taking steam, argon, methane, ethane, nitrogen and the like as diluent materials to be mixed with the low-carbon alkane and then introduced into the reactor, wherein the preferred diluent material is hydrogen. When hydrogen is selected, the molar ratio of hydrogen to the light alkane is preferably 0.1-10: 1. more preferably 0.3 to 3:1.
the low-carbon alkane is C 3 ～C 5 Such as propane, butane or pentane, said butane being n-butane or isobutane.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
In the examples and comparative examples, the concentration of elements in catalyst pellets was analyzed by an electron probe technique, the catalyst was cut into hemispheres, and the element content was measured by uniformly taking 40 points from the center to the outer edge of the sphere.
Example 1
(1) The alumina carrier of the invention is prepared.
27g of an aluminum sheet was taken, and 610 g of a hydrochloric acid solution having a concentration of 18 mass% was added to dissolve the aluminum sheet, thereby obtaining a solution having an aluminum trichloride content of 4 mass%. The aluminum trichloride solution is transferred into a neutralization tank, 850 g of ammonia water with the concentration of 6 mass percent is added, and the mixture is uniformly mixed at the temperature of 60 ℃, and the pH value is 7.5-8.5. The generated aluminum hydroxide is filtered and washed, and 9mL of the aluminum hydroxide with the volume ratio of 1:1 to obtain sol.
To the sol were added 40mL of a solution containing 30 grams of urea and a hydrochloric acid solution containing 0.32 grams of stannous chloride with stirring to give a solution containing Sn in an amount of 0 on a dry basis of alumina.30% by mass, stirred for 1 hour and acidified. Then 30 g of kerosene and 3 g of fatty alcohol-polyoxyethylene ether were added dropwise to the acidified sol with stirring. Dropping the sol into oil ammonia column with oil phase in the upper layer and ammonia water phase in the lower layer. The oil phase is kerosene, and the concentration of ammonia water in the ammonia water phase is 8 mass%. Solidifying the wet ball in an ammonia water phase for 1 hour, taking out and washing with deionized water, drying at 60 ℃ for 6 hours, drying at 120 ℃ for 10 hours, roasting at 650 ℃ for 4 hours in air flow for one time, then treating at 650 ℃ in air with the water vapor content of 5 volume percent for 10 hours, heating to 1000 ℃ and roasting for 4 hours for two times to obtain the spherical theta-Al containing tin 2 O 3 The average diameter of the carrier and the alumina pellets was 1.6mm.
The specific surface area of the carrier was 118m 2 The pore volume is 0.70mL/g, the pore volume of 2-10 nm in the carrier accounts for 13.1 percent of the total pore volume, the pore volume of 10-20 nm accounts for 50 percent of the total pore volume, the pore volume of 20-50 nm accounts for 1.8 percent of the total pore volume, and the pore volume of 50 nm-10 mu m accounts for 35.1 percent of the total pore volume.
(2) Preparation of the catalyst
Taking the above-mentioned tin-containing theta-Al 2 O 3 The pellets were immersed in an immersion liquid containing chloroplatinic acid and hydrochloric acid at 25 ℃ for 4 hours, the immersion liquid containing 0.30 mass% of platinum and 1.2 mass% of HCl (both relative to the mass of dry alumina, the same applies hereinafter), and the liquid/solid ratio was 1.8mL/g. The impregnated solid was dried at 120 ℃ for 12 hours and calcined at 500 ℃ for 4 hours.
The calcined solid was immersed in a potassium nitrate solution as an immersion liquid at 25 ℃ for 4 hours, the immersion liquid containing 1.0 mass% of potassium (relative to the mass of dry alumina) and having a liquid/solid ratio of 2.0mL/g. The impregnated solid is dried at 120 ℃ for 12 hours, roasted at 600 ℃ for 4 hours, and reduced with hydrogen at 550 ℃ for 4 hours to obtain the catalyst A.
The content of platinum, the content of tin, the content of potassium and the content of chlorine in the catalyst a were 0.30 mass%, 1.0 mass% and 1.02 mass%, respectively (both with respect to the dry alumina, the same applies hereinafter). The radial distribution of Pt in the pellets of catalyst A is shown in FIG. 2 for 1,K and for Sn in FIG. 3.
As can be seen from fig. 1 to 3, 99 mass% of Pt was distributed in the surface layer of the spherical carrier having a thickness of 420 μm from the outside to the inside, 99 mass% of K component was distributed in the surface layer of the spherical carrier having a thickness of 450 μm from the outside to the inside, and Sn component was uniformly distributed in the spherical carrier.
Example 2
A catalyst was prepared by the method of example 1 except that (2) a tin-containing theta-Al was impregnated with an impregnation solution containing chloroplatinic acid and hydrochloric acid 2 O 3 In the case of pellets, the impregnation solution contained 0.30 mass% of platinum and 1.5 mass% of HCl, and the catalyst B was prepared so as to have a platinum content of 0.30 mass%, a tin content of 0.30 mass%, a potassium content of 1.0 mass% and a chlorine content of 1.05 mass%, and the radial distribution of Pt in the pellets of the catalyst B is shown in fig. 2 for 1,K and the radial distribution of sn is shown in fig. 3.
As can be seen from fig. 1 to 3, 99 mass% of Pt was distributed in the surface layer of the spherical carrier having a thickness of 400 μm from the outside to the inside, 99 mass% of K component was distributed in the surface layer of the spherical carrier having a thickness of 420 μm from the outside to the inside, and Sn component was uniformly distributed in the spherical carrier.
Example 3
A catalyst was prepared as in example 1, except that (2) a tin-containing theta-Al was impregnated with an impregnating solution containing chloroplatinic acid, hydrochloric acid and trichloroacetic acid 2 O 3 The impregnation solution contained 0.30 mass% of platinum, 0.50 mass% of HCl, and 1.5 mass% of trichloroacetic acid (both relative to the mass of dry alumina), and the catalyst C thus obtained contained 0.30 mass% of platinum, 0.30 mass% of tin, 1.0 mass% of potassium, and 1.05 mass% of chlorine. The radial distribution of Pt in the small balls of the catalyst C is shown in 1,K in FIG. 2, and the radial distribution of Sn is the same as that of the catalyst A and is uniformly distributed in the spherical carrier.
As can be seen from FIGS. 1 and 2, 99 mass% of Pt was distributed in the surface layer of the spherical support having a thickness of 500 μm from the outside to the inside, and 99 mass% of K component was distributed in the surface layer of the spherical support having a thickness of 450 μm from the outside to the inside.
Comparative example 1
The catalyst was prepared by following the procedure of example 1 except that (2) the tin-containing theta-Al was impregnated with an impregnation solution containing chloroplatinic acid and hydrochloric acid 2 O 3 In the case of pellets, the impregnation solution contained 0.30 mass% of platinum and 2.0 mass% of HCl, and the catalyst D thus obtained contained 0.30 mass% of platinum, 0.30 mass% of tin, 1.0 mass% of potassium and 1.07 mass% of chlorine. The radial distribution of Pt in the pellets of catalyst D is shown in FIG. 2 for 1,K and in FIG. 3 for Sn.
As can be seen from FIGS. 1 to 3, the metal components are uniformly distributed in the pellets of the catalyst D.
Comparative example 2
A catalyst was prepared as in example 1, except that (2) a tin-containing theta-Al was impregnated with an impregnating solution containing chloroplatinic acid, hydrochloric acid and trichloroacetic acid 2 O 3 The impregnation solution contained 0.30 mass% of platinum, 1.0 mass% of HCl, and 5.0 mass% of trichloroacetic acid (both relative to the mass of dry alumina), and the catalyst E thus obtained contained 0.30 mass% of platinum, 0.30 mass% of tin, 1.0 mass% of potassium, and 1.05 mass% of chlorine.
The radial distribution of Pt in the pellets of catalyst E is shown in FIG. 1,K in FIG. 2 and the radial distribution of Sn is the same as for catalyst A. In the pellets of catalyst E, the metal components were uniformly distributed.
Examples 4 to 8
In a micro-reactor, 2 ml of catalyst is loaded, the mixed gas of hydrogen and propane is used as raw material, the temperature is 620 ℃, the pressure is 0.21MPa, and the propane feeding mass space velocity is 3.5h -1 Hydrogen/propane molar ratio 0.5:1 for 35 hours, and samples were taken every 1 hour for chromatography to calculate the propane conversion and propylene selectivity, the results of which are shown in table 1.
As can be seen from Table 1, the catalyst of the present invention has higher propane conversion rate and propylene selectivity, better performance stability, and lower carbon deposition after 35 hours of reaction, compared with comparative catalysts D and E, indicating that the catalyst of the present invention has excellent reaction performance.
TABLE 1
Figure BDA0001845553910000081

Claims (13)

1. A low-carbon alkane dehydrogenation catalyst comprises a spherical theta-alumina carrier and active components with the following contents calculated by taking the carrier as a reference:
0.1 to 2.0 mass percent of metal in the VIII group,
0.1 to 2.0 mass% of the second metal component,
0.5 to 2.0 mass% of a group IA metal,
0.3 to 3.0 mass% of chlorine,
the average diameter of the spherical theta-alumina carrier is 1.5-2.0 mm, the group VIII metal and the group IA metal are distributed in a surface layer of which the thickness is 350-500 mu m from outside to inside of the spherical carrier, and the second metal component is uniformly distributed in the carrier and is selected from tin, germanium, lead, indium, gallium or thallium.
2. The catalyst according to claim 1, wherein the content of the group VIII metal is 0.1 to 1.0 mass%, the content of the second metal component is 0.1 to 1.0 mass%, the content of the group IA metal is 0.5 to 2.0 mass%, and the content of chlorine is 0.3 to 2.0 mass%.
3. The catalyst according to claim 1 or 2, characterized in that in the theta-alumina carrier, the pore volume of pores with diameters of 2 to 10 nanometers accounts for 4 to 15 percent of the total pore volume, the pore volume of pores with diameters of 10 to 20 nanometers accounts for 40 to 60 percent of the total pore volume, the pore volume of pores with diameters of 20 to 50 nanometers accounts for 1.0 to 5.0 percent of the total pore volume, and the pore volume of large pores with diameters of more than 50 nanometers but not more than 10 micrometers accounts for 20 to 50 percent of the total pore volume.
4. A catalyst according to claim 1 or claim 2 wherein the group viii metal is platinum and the group IA metal is potassium.
5. The catalyst according to claim 1, wherein the spherical θ -alumina carrier has a specific surface area of 50 to 130m 2 The pore volume is 0.6 to 0.75 ml/g.
6. The catalyst of claim 1 wherein the lower alkane is propane, butane or pentane.
7. A preparation method of the low-carbon alkane dehydrogenation catalyst as claimed in claim 1, which comprises the steps of impregnating a spherical theta-alumina carrier containing a second metal component with a mixed solution containing a VIII group metal compound and a competitive adsorbent, wherein the competitive adsorbent is hydrogen chloride or a mixture of hydrogen chloride and chloroacetic acid, when the competitive adsorbent is hydrogen chloride, the mass ratio of the competitive adsorbent contained in an impregnating solution to the alumina carrier is 1.1-1.8%, when the competitive adsorbent is a mixture of hydrogen chloride and chloroacetic acid, the mass ratio of hydrogen chloride contained in the impregnating solution to the alumina carrier is 0.2-0.8%, the mass ratio of chloroacetic acid to the alumina carrier is 1.2-2.0%, and the impregnating solution/solid ratio is 1.3-3.0 ml/g, drying and roasting the impregnated solid, then impregnating with a solution containing an IA group metal compound, drying, roasting and reducing.
8. The method of claim 7, wherein the chloroacetic acid is dichloroacetic acid or trichloroacetic acid.
9. A process according to claim 7 wherein the group VIII metal compound is chloroplatinic acid or ammonium chloroplatinate and the group IA metal compound is a hydroxide, nitrate or chloride of a group IA metal.
10. A process according to claim 9, wherein the hydroxide of a group IA metal is potassium hydroxide, the nitrate of a group IA metal is potassium nitrate and the chloride of a group IA metal is potassium chloride.
11. A method according to claim 7, wherein the second metal component of the second metal component-containing alumina support is introduced during the formation of the support or by impregnation after the formation of the support.
12. A process according to claim 11, characterised in that the compound used to introduce the second metal component into the alumina support is stannous bromide, stannous chloride, stannic chloride pentahydrate or tetrabutyltin.
13. The method according to claim 7, wherein the reduction temperature is from 450 ℃ to 700 ℃ and the reduction time is from 0.5 to 20 hours.
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