United States Patent [191 Juguin et al.

[111 4,401,557 [451 Aug. 30, 1983

[54] CATALYSTS FOR HYDROCARBON CONVERSION

[75] Inventors: Bernard Juguin, Rueil Malmaison; Germain Martino, Poissy; Jean , Miquel, Paris, all of France

Societe Francaise Des Produits Ptiur Catalyse, Rueil Malmaison, France

[21] Appl. No; 616,123 [22] Filed: Sep. 24, 1975

[30] Foreign Application Priority Data Sep. 25, 1974 [FR] France .............................. .. 74 32576

[51] Int. Cl.3 ...................... .. c100 35/09; B01J 27/06 [52] us. 01. .................................. .. 208/139; 252/441;

252/458; 252/461; 252/465; 252/466 PT; 252/470

[58] Field 61" Search .............. .. 208/139; 252/441, 458, 252/461, 465, 466 PT, 470

[73] Assignee:

[5 6] References Cited U.S. PATENT DOCUMENTS

3,898,154 8/1975 Rausch .............................. .. 208/139 3,956,103 5/1916‘ .Qntos 208/139 3,960,709 6/1976 Hayes ................................ .. 208/139

Primary Examiner-,-Curtis R. Davis Attorney, Agent, or Firm-Millen & White

[57] _ ABSTRACT

Reforming process operated in the presence of a cata lyst comprising a carrier, platinum, rhodium or osmium, an additional metal consisting of chromium, tungsten, molybdenum, manganese, rhenium, germanium, tin, gallium, indium, thallium, thorium, cerium, Samarium, lanthanum, zinc, cadmium, titanium or zirconium, and halogen. ‘

42 Claims, No Drawings

4,401,557 1.

CATALYSTS FOR HYDROCARBON CONVERSION

This invention concerns a catalytic reforming process in which the catalyst comprises (a) a carrier, (b) plati num, .(c) atleastonemetal selected frm rhodium and osmium and (d) at least a third additional element se lected from the groupconsisting of: chromium, tung sten, molybdenum, manganese, rhenium, germanium, tin, gallium, indium, thallium, thorium, cerium, samar ium, lanthanum, zinc, cadmium, titanium and zirco nium. ' . .

Processes for reforming’in the presence of catalysts containing platinum deposited on a carrier have been known for a long time. But, in spite of many improve ments brought to these catalysts having a platinum base, for example, by incorporating a second metal such as tungsten, molybdenum, rhenium, germanium, iridium, etc, efforts are devoted, even nowadays, to ?nd cata lysts with a platinum base which, on the one hand, would give better yields as those obtainedup to now and, on the other hand, would have a longer life than that of the known catalysts. Efforts are also devoted to ?nd catalysts having improved mechanicalproperties; in fact, the reforming catalystsare conventionally em ployed in ?xed or movable bed, intthe form of conglom erates, for example balls or extrudates, of appreciable size, thus leaving a sufficient passage to gaseous reac tants. Weanof these catalysts results in the formation of far smallerparticles which progressively clog the free space and oblige toincrease the reactant inlet pressure or even tostopthe operation. , Now, although it was known that high yields are

obtained, particularly in reforming reactions, by using catalysts comprising a porous carrier, for example alu-, mina, and platinum in association with rhodium or os mium, we have now found that the so-de?ned catalysts have an increased reforming activity and, above all, a longer life time, when a third additional metal is incor porated to the metal system, said additional metal being selected from: chromium, tungsten, molybdenum, man-,. ganese, rhenium, germanium, tin, gallium, indium, thal lium, thorium, cerium, samarium, lanthanum, "zinc, cad mium, titanium and zirconium. _ , "

’ Theyields then remain unchanged over An essential feature of reforming process conforming

to the invention lies in the‘ usefof a catalyst comprising a carrier and '(a) platinum, (b) rhodium or osmium, (c) an additional element selected ‘from the group consist ing of ‘chromium, tungsten, molybdenum, manganese, rhenium, germanium, tin, ‘gallium, indium, ‘ thallium, thorium, cerium, samarium, lanthanum, zinc, cadmium, ‘ titanium ‘and zirconium, and (d) a halogen, for example chlorine or ?uorine. V c ' i ,

The carrier mainly ‘contains an oxide‘ofhan element from groups II, III and IV of the periodic classi?cation of elements, for example alumina, silica,_alumina-silica, magnesia, magnesia-silica, magnesia-alumina, thorium oxide-silica, etc. ,

A particularly suitable carrier is alumina. , i The catalyst thus employed in the processaccording

to the invention‘contains, by weight with respect to the

long periods.

20

25

30

35,

40

45. i

(.60.

catalyst carrier, from 0.005 to 1% and more particularly _. from 0.05 to 0.8% of platinum, vfrom.0.005 to 1% and more particularly from 0.01 to 0.9% of rhodium or osmium ‘(if desired 0.02—0,8% of rhodium or osmium) and from 0.005 to 5%, preferablyjfrom 0.01 to 4%, and more particularly from, 3% of one metal from I

2 the above-mentioned .group, i.e. chromium, tungsten, molybdenum, manganese, rhenium, germanium, tin, gallium, indium, thallium, throium, cerium, samarium, lanthanum, zinc, cadmium, titaniumand zirconium. The catalyst also contains 0.1 to (10% and preferably

0.2 to 5% by weight, with respect to the catalyst carrier, of halogen, for example chlorine or ?uorine. The texture characteristics of the catalyst carrier may

also have an effect: the speci?c surface of the carrier mayv usefully range from 50 to '600 m2 per gram, prefera bly from 150 to 400 m2/ g, in order to be able to work at reasonably high space velocities and to avoid the re course to reactors of too big size and the use of exces sive amountsof catalyst. The invention also concerns a new catalyst, which

may be used, for example, in reforming and comprises alumina and, by weight, with respect to alumina: (a) 0.005-1% of platinum, (b) 0.005—l% of rhodium or osmium, (o) 0.05-3% of an additional metal selected from the group consisting of chromium, tungsten, mo lybdenum, manganese, rhenium, germanium, tin, gal lium, indium, thallium, samarium, zinc, cadmium, tita nium and zirconium, and (d) 0.1-10% of halogen.

‘ The catalyst may be prepared according to conven tional methods by impregnating the carrier by means of solutions of the metal compounds whose supply is de sired.- There is used either a common solution of these metals-or distinct solutions for each metal. When using several solutions, intermediate dryings and/ or roastings may be performed. Roasting, which is the usual ?nal stop, is conducted for example at about 500°—1.000° C., preferably in the presence of free oxygen, for example, by scavenging with air.

Platinum may be used in any known form, for exam ' ple, as hexachloroplatinic acid, ammonium chloroplati nate',‘plati'num sul?de, sulfate or chloride. Rhodium and osmium may be used in any known form, for example, as chloride, bromide, sulfate of sul?de, or in the form of, for example, acetylacetonate, osmic acid, chlorosmic acids, etc. Examples ofv compounds of additional metals are

nitrates, chlorides, ‘bromides, ?uorides, sulfates or ace tates of these metals, or- any other salt or oxide of these metals, soluble in water, hydrochloric acid or other convenient solvent (for example, chromates, molyb dates, tungstates, etc.). Heteropolyacids and organic and inorganic complexes containing these additional metals (acetylacetonates, alkyl tin, oxalic, tartric, citric and other complexes, etc.) are also worth to mention. Halogen may be supplied as one of the above men

tioned halides. or as hydrochloric acid, hydro?uoric acid, ammonium chloride, ammonium ?uoride, gaseous chloride or hydrocarbon halide, for example CCl4,

, CHC13 or CH3C1. ‘ .

A ?rst method of manufacture comprises, for exam~ ple, impregnating the carrier with an aqueous solution of nitrate or any other compound of the selected addi tional metal (other than platinum and rhodium or os mium), drying at about 120° C. and calcining in air for a few hours at a temperature of 500°-1000° C., prefera bly at about 700° C.; then‘ follows a second impregna tion with a solution containing platinum and rhodium or osmium (for example a solution. of hexachloroplatinic

, acid, rhodium trichloride or osmic acid). , ,

Another method consists, for example, of impregnat ing the carrier with a solution of: , ~

(1) platinum (for example hexachloroplatinic acid),

4,401,557 3

(2) rhodium or osmium (for example rhodium trichlo-' pride, osmic acid) > 1 ‘

(3) the selected additional metal (for example, a chlo ride, bromide, ?uoride, sulfate or acetate of the se lected metal, or any other salt or oxide of the selected .metal, soluble_~,-in water, hydrochloric acid or any other suitable solvent, for example a chloroplatinate, an acetylacetonate, etc.), and .

(4) chlorine or fluorine. , Av further method comprises introducing the metal

elements by effecting as many successive impregnations as the number of metal elements to be included in the catalyst; for example, rhodium or osmium is ?rst intro duced by means of a solution thereof, optionally fol lowed with drying and roasting, . then platinum by means of a solution thereof, optionally

followed with drying and roasting, and ?nally the selected additional metal, in any of the

various forms as previously indicated, the latter im pregnation being followed with drying and roasting at a temperature of, for example, about 500°—1,000° C. It is stated that the above sequence of impregnations

is not compulsory and may be altered. vThe catalysts thus obtained are used in reactions of

catalytic reforming. These reactions are usually carried out at a temperature of about 450°-580° C., a pressure of about 5—20 kg/cm2 and a hourly reaction rate usually in the range of 0.5—10 volumes of liquid charge (naphtha distilling at about 60°—220° C.) per volume of catalyst. The following examples illustrate the invention while

not limiting the scope thereof.

EXAMPLE 1

Catalysts A-R are, prepared, which all exhibit a spe~ ci?c surface of 230 m2/ g, a pore volume of 54 cc/ g and a chlorine content of 1.14%. Catalysts A-R all contain 0.20% of platinum, 0.05% of rhodium and 0.50% .of a third metal element as de?ned herein after for each of the catalysts A-R: ~

' A —' chromium I —- thallium

B —— molybdenum K -— germanium

C — tungsten . L —- tin

‘ D —- manganese M —— thorium

E — rhenium N — cerium

F — zinc O — Samarium

G — cadmium 1' P — lanthanum

H — gallium Q — titanium

I — indium R — zirconium

Catalysts A-R were all prepared with alumina of a 240 m2/ g speci?c surface and a 59 cc/g'pore volume. Catalyst A was prepared by adding to 100 g of alu->

mina 100 cc of an aqueous solution of 0.96 g chromic anhydride (CrO3) 2.24 g concentrated HCl (d: 1.19) 8 g of an aqueous solution of rhodium trichloride con

taining 2.5% b.'w. of Rh. ‘ 1

After a 5 hours contact, ?ltration and drying at 100° C., the catalyst is roasted for 4 hours a't'530° C. in dry air ‘' (dryingwith activated alumina) and reduced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C , v

The resulting‘ catalyst contains, by weight with‘re; spect to the catalyst carrier: - 0.20% ofplatinum ‘ 0.05% of rhodium 0.50%‘0f chromium

25

30

40

'45

50

60

65

4 1.14% of chlorine. Catalyst D was prepared by admixing 100 g of alu

mina with 100 cc of an aqueous solution containing: 2.30 g of manganese nitrate Mn(NO3)2(6H2O) 2.24 g of concentrated HCl (d=1.19) 8 g of an aqueous solution of chloroplatinic acid con

taining 2.5% b.w. of Pt 2.00 g of an aqueous solution of rhodium trichloride

containing 2.5% b.w. of Rh. The components were contacted for 5 hours, ?ltered,

dried for 1 hour at 100° C., calcined for 4 hours at 530° C. in dry air (drying with activated alumina) and re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by weight with re

spect to the catalyst carrier: ‘ 0.20% of platinum 0.05% of rhodium 0.50% of manganese 1.14% of chlorine. Catalyst F was prepared by adding to 100 g of alu

mina, 100 cc of an aqueous solution containing: 0.22 g of zinc sulfate (ZnSO4, 71-120) 2.24 g of concentrated HCl (d: 1.19) 8 g of an aqueous solution of chloroplatinic acid con

taining 2.5% b.w. of platinum 2 g of anaqueous solution of rhodium trichloride con

taining 2.5% of rhodium. ‘ The components were contacted for 5 hours, ?ltered,

dried for 1 hour at 100° C., roasted for 4 hours at 530° C. in dry air (drying with activated alumina) and re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. ‘

The resulting catalyst contains, by weight with re spect to the catalyst carrier: 0.20% of platinum 0.05% of rhodium 0.50% of zinc 1.14% of chlorine. ,_ . Catalyst H was prepared by adding to 100g of alu

mina 100 cc of an aqueous solution of: I a

10 cc of gallium nitrate as a solution containing 50 g of gallium per liter

2.24 g of concentrated HCl (d=1.19) , . 8 g of an aqueous solution of chloroplatinic acid con

taining 2.5% b.w. of platinum 2.00 g of an aqueous solution of rhodium trichloride

containing 2.5% b.w. of Rh. ,, The components were contacted for 5 hours, ?ltered,

dried for-1 hour at 100° C., calcined for 4 hoursat 530° C. in dry air (drying with activated alumina) and then reduced in a stream of dry hydrogen (activated alu mina) for 2 hours at 450° C. The resulting catalyst con tains, by weight with respect to the catalyst carrier: 0.20% of platinum 0.05% of rhodium 0.50% of gallium 1.14% of chloride. Catalyst L was prepared by adding to 100 g of alu

*mina 100 cc of an aqueous solution of: 2.6 g of a tin acetic solution containing 22% of tin, 2.24- g of concentrated HCl (d: 1.19) 8.0 g of an aqueous solution of chloroplatinic acid con

_ taining 2.5% aw. of Pt 2.0 g of an aqueous solution of rhodium trichloride

containing 2.5% b.w. vof Rh. The components were contacted for 5 hours, ?ltered,

dried for 1 hour at 100° C., roasted for 4 hours at 530°

4,40 1,55 '5'7 5»:

C. in dry ‘air‘ (dr'yi‘n'g"with activatedialumi‘na) an‘dl‘thenl reduced in a stream of dry hydrogen“ (activated ‘alu-r mina) for 2 hours" at'450‘ 'C. The‘resultin'g catalyst con tains, by weight with respect to the catalystcarrier: ‘0.20% ofplar'iiiuiui - 1 5 l ~ ~ '1

0.05% of rhodium" ‘ _ ‘~‘ ' n _

0.50% of tiiri“ - ' ‘ l.l4%*of chlorine ' ' i " '

“Catalyst P was prepared by""adding ‘to I00 'g'of ‘alu-_ mina, 100 cc of an aqueous solution‘of: ' " 5 g of a solution of lanthanum nitrate’c’iontainingl0% of lanthanum ' 'l“ ' '

2.24 g of concentrated HCl ((1: 1.19) . . 8 g of an aqueous solution of chloroplatinic acid con

taining 2.5% b.w. qflplatinum _ ‘ " a

2 g of_ an‘ aqueous sollition'of rhodium trichloride con taining 2.5% of Rh.‘ ' ‘ w’ The components are contacted for 5 hours, ?ltered,

dried for ‘lv hour at l00°WC., roastedhfor 4 hours at 530° C. in dry air (drying with activated alumina) and then reduced in a stream of dry hydrogen ‘(activated alu mina) for 2 hours at 450° C. The resultingcatalyst con tains, by weight with respect to the catalystcarrier: 0.20% of platinum . -

- I

i

n 0.50% of ‘lanthanum. .' 1 . . i

. 1.14%.of chlorine. _

Catalyst R;was prepared by adding-‘to 100 of alu-' mina 100 cc of an aqueous solution containingzl 6.67 g of a zirconium oxychlorine solution ‘containing 7.5% of zirconium ' - . i ' 'i

2.24 g of concentrated HCl (d=1.19)-: - l 8 g of 'an aqueousisolution-of chloroplatinic ‘acid con

taining 2.5%-b.w. of Pt. ‘ ‘ » ~ i- i

2.00 g ‘of an‘ aqueous solution of rhodium trichloride containing 2.5% b.w. of Rh. i1 ' ‘ ' l ' '

The components’we'ré contacted for 5 hours, ?ltered, dried for l’li'our at l00°v C., roasted fort-'4 hours at1‘530°' C. in dry air (drying with activated alumina) and "then reduced‘in a stream of'dry hydrogen (activated'alu~ mina) for 2 hours at 450° C. The resul't'ingcatalyst con tains, by weight with‘ respect to'the catalyst carrier:

' ‘0.20%“bf platinum‘ ; l ' ' '7 ' " i 0.05% of rhodium

0.50% of ‘zirconium 1.14% bf chlorin'ell'" ‘ N , I I

The other cataly'sts have bee?lp‘repa'red in thesa'me was according to similar methodswhijchne'ed not to be described herein with further details. 1',“ v A. l; The naphtha to be treated has the ‘following specifica

tions: , f. r. ,i . -ll.

“Distillation A‘Jsrlvl. ‘ 804160“ C; l Composition: aromatic hydrocarbons 7% by weight " l 1

naphthenic hydrocarbons 12s 27% by weight 3 ~paraf?nichydmcarbons 4‘. v i 66% by weight _ Clear Research; octane number ‘ about 37 7 Average molecular weight 110

0.782 Density at 20° C. qt; if *

This naphtha‘ is’ passed with recyclefhly'drogen on the various alumina-containing catalysts A-R whose metal composition is given again in .Table I ~ i ~ >

Theloperation is so conducted as to obtain a‘ clear octane number qf{96.2. The experimental conditions are as follows: ‘ '- i

IO

15

. .. . ‘25.

0.05% ofrhodium ‘ _ i. .- s

30

35

Pressure H. _ 20 bars;

Molar I'll/hydrocarbons ratio ‘ 5 Weight of naphtha/weight of catalyst/hour 2 ‘ 3 V‘

The reactorinletitemperature is. 490°il'7a C. ltrsuf ?ces to raise it progressively .to. 530° ‘C. to maintain a constant octane number. 7 V.‘ a

Table I gives,‘ for catalysts A—R.,as used, the ‘C5‘+_ yield‘ and the % hydrogen ‘in the recycle gas when the desired octane number has been obtained.

--‘- ' " l‘ -TABLEI ‘ ‘ l

( 3 _ “ Recycle

a‘ "CATALYST ‘ Yield ‘ - gas’! ‘

»%by weight“‘-' -% C5+ % Hrv % Pt % Rl'ii'% additional metal' I by weight by mole

A "022 0.05 -‘ 0.5% Chromium 22.2' ‘ 82.2 B 0.2 0.05 0.5% Molybdenum 82.3 .225‘ C 0.2, 0.05 . 0.5% Tungsten 82.6 82.71 D 0.2 0.05 0.5% Manganese 82.4 82.3 1

E 0.2 0.05 0.5%-medium _ 82.4 82.3 ‘ F 0.2 0.05 0.5% Zinc - 82.3 82.2 G 0.2 0.05 0.5% Cadmium ‘82.3 82.4 H 0.2 0.05 0.5% Gallium - 82.5 82.4. I 0.2 0.05 0.5% Indium 82.3 82.5 J 0.2 0.05 0.5% Thalliurn 82.2 _ ,s2.41 K 0.2 0.05 0.5% ‘Germanium 82.6 82.6’ L 0.2 4-‘005 ' 0.5% Tin 82.6 82.4 M 0.2 0.05 0.5% Thorium 82.4 82.4 N 0.2 0.05 0.5% Cerium 32.4 {-82.3 0 n 0.2 0.05 0.5% Samarium I 82.4 v 82.4 P 0.2 0.05 0.5% Ilanthanum“ 82.4 ' 82.3 Q 0.2 0.05 0.5% Titanium 82.5 82.3 R 0.2 0.05 0.5% Zirconium 82.6 ' 82.2

‘ Catalysts ai-i ‘have been :prepared; their composition and properties are identical to those of catalysts“ A_-R‘ ex'cept'that‘wliodiilm ‘has been replaced by osmium‘in their ‘composition. " ' '

All of catalysts a-r contain 0.20% of platinum; 0.05%» 40 of osmium and 0.50% off‘a'thirdelement‘ as stated for

45

55

each of the catalysts.a—r:

a —— chromium j — thallium

b —— molybdenum i k — germanium .

' f-zinc o-"sa‘marium‘lw

g — cadmium 1. p —- lanthanum

h -— gallium q ,— titanium _ n a

i — indium r - zirconium ‘ _

Catalysts a-r have all‘ been prepared witlr alumina. having a speci?c surfacenof 240 m2/ g and a pore volume

of 59 cc/g.- ;~ " ~ A - -l ‘. 9-‘ Catalyst a was prepared by adding to 100 g of ‘alu-.

mina 100 ,ccof'an aqueous‘ solution containing: 1 096g o?ichrornic. anhydride (CrO3) 2.24rgzof concentrated HCl (d=’l=.l9) i 8 g of an aqueous chloroplatinic acid solution of 2.5%

b.w. Pt content. s " i i

2.00 g of an aqueous chlorosmic acid‘ solution of 2.5% b.w. 05 content. ‘ > 1

The components were contacted for 5 hours, ?ltered, dried for v1 hour at 100“ ‘C5, roasted for 4 hours at 530° C. in dry air (dried with'activatedlalumina), then re duced in 'a‘str'eam of dry hydrogen (activated alumina)‘ for 2 hours at 450° C. 1

4,401,557 The resulting catalyst contains, by weight with re

spectto the catalyst carrier: 0.20% of platinum 0.05% of osmium _.

0.50% of chromium 1.14% of chlorine. Catalyst d was prepared by adding to 100 g of alu

mina 100 cc of an aqueous solution containing: 2.30 g of manganese nitrate Mn(NO3)‘2(6I-12O) 2.24 g of concentrated HCl (d: 1.19) 8 g of an aqueous chloroplatinic acid-solution of 2.5%

b.w. Pt content. -' 2.00 g of an aqueous chlorosmic acid solution of 2.5%

b.w. Os content. '

The components were contacted for 5 hours, ?ltered, dried for 1 hour at 100° C., roasted for 4 hours at 530° C. in dry air (dried with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by weight with re

spect to the catalyst carrier: 0.20% of platinum 0.05% of osmium 0.50% of manganese 1.14% of chlorine. Catalyst f was prepared by adding to 100 g of alu

mina, 100 cc of an aqueous solution containing: 0.22 g of zinc sulfate (ZnSO4, 71-120) 2.24 g of concentrated HC] (d=1.19) 8 g of an aqueous chloroplatinic acid solution of 2.5%

b.w...Pt content. 2 g of an aqueous chlorosmic acid solution of 2.5% Os ‘content. The components were contacted for 5 hours, ?ltered,

dried for l‘hour at ‘100° C., roasted for 4,,hours at 530°‘ C. in dry ,air (drying with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. _

The resulting catalyst contains, by weight with re spect to the catalyst carrier: 0.20% of platinum 0.05% of osmium 0.50% of zinc .

1.14% of chlorine. ‘ -

Catalyst h was prepared by adding to 100 g of alu mina 100 cc of an aqueous solution containing: 10 cc of gallium nitrate as a solution containing 50 g of gallium per liter.

2.24 g of concentrated HCl (d: 1.19,) 8 g of an aqueous chloroplatinic acid solution of 2.5%

b.w. Pt content. 2.00 g .of an aqueous chlorosmic acid solution of 2.5% .-b.w. Os content. . -

The components were contacted for 5 hours, ?ltered, dried for 1 hour at 100° C., roasted for 4 hours at 530° C. in dry air (dried with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by’ weight with respect to the catalyst carrier: 0.20% of platinum - 0.05% of osmium 0.50% of gallium 1.14% of chlorine. . Catalyst 1 was prepared by adding to 100 g of alu

mina, 100 cc of an aqueous solution containing: ‘2.6 g of tin acetate solution of 22% tin content 2.24 g of concentrated HCl ((1: 1.19) > ‘

5

10

20

25

30

35

40

45

50

60

65

8 8 gjof an aqueous chloroplatinic acid solution of 2.5%

‘ b.w. Pt content.

2.00 g of an aqueous chlorosmic solution of 2.5% b.w. 05 content. ,

The components were contactedv for 5 hours, ?ltered, dried for 1 hour at 100° C., roasted for 4 hours at 530° C. in dry air (dried with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by weight with respect to the catalyst carrier: 0.20% of platinum 0.05% of osmium 0.50% of tin 1.14% of chlorine. Catalyst p was prepared by adding to 100 g of alu

mina, 100 cc of an aqueous solution containing: 5.00 g of a lanthanum nitrate solution of 10% lanthanum

content 2.24 g of concentrated HCl (d=1.19) 8 g of an aqueous chloroplatinic acid solution of 2.5%

b.w. Pt content 2.00 g of an aqueous chlorosmic acid solution of 2.5%

vb.w. Os content. The components were contacted for 5 hours, ?ltered,

dried for 1 hour at 100° C., roasted for 4 hours at 530” C. in dry air (dried with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by weight with respect to the catalyst carrier: 0.20% of platinum 0.05% of osmium 0.50% of lanthanum 1.14% of chlorine. Catalyst r was prepared by adding to 100 g of alumina

100 cc of an aqueous solution containing: 6.67 g of a zirconium oxychrloride solution of 7.5%

zirconium content 2.24 g of concentrated HCl (d=1.19) 8 g of an aqueous chloroplatinic acid solution of 2.5%

b.w. Pt content I

2.00 g of an aqueous chlorosmic acid solution of 2.5% b.w. Os content. 7 The components were contacted for 5 hours, ?ltered,

dried for 1 hour at 100° C., roasted for 4 hours at 530° C. in dry air (dried with activated alumina), then re duced in a stream of dry hydrogen (activated alumina) for 2 hours at 450° C. The resulting catalyst contains, by Weight with respect to the catalyst carrier: 0.20% of platinum " ‘0.05% of osmium 0.50% of zirconium’ 1.14% of chlorine. The other catalysts were prepared in the same man

ner, according to similar methods, and they were tested in 'the same‘ manner'as previously described and with the same naphtha as previously de?ned.

Table 11 gives, for the catalysts a-r, the C5+ yield and the % hydrogen contained in the recycle gas when the desired octane number has been attained.

TABLE I1 Recycle

, CATALYST Yield gas _ % by weight % C5Jr % H2

“% Pt % Os % additional metal by weight by mole

a 0.2 0.05 0.5% Chromium 82.3 82.2 b ' 0.2 _ 0.05 0.5% Molybdenum 82.2 82.5 C. ' 0.2 0.05 0.5% Tungsten ' 82.6 82.6 d 0.2 0.05 0.5% Manganese 82.4 82.4

4,401,557 ‘ 9. 10

TABLE II-continued TABLE IV . ‘Recycle ‘ _ Recycle

CATALYST yield gas CATALYST Yield gas % by weight ' % c5+‘ ' ' _% it; % Pry we‘gh‘ ‘ % ‘35+ % H1

% Pt % Os % additional metal by weight by mole % P! %‘Rh i%_ éddmona] metal a by we'ght by mole . ' A" 0.2 0.05 0.08% Chromium i‘ ‘ 82.1 82.]

i 3'8: 3'2: gi‘emum B‘! 0.2 0.05 0.08%M01yb0enuni ‘ 82.2 82.4 ' ' ' " ‘"C _ ' ~ c" 0.2 0.05 0.08% Tungsten 82.5 82.5

g 0'2 0505 ‘05% Cad'f‘mm 82-3 . 821 D" 0.2 g 0.05 0.08% Manganese 82.4 _ 82.2 h 02 °~°5 05% Gallium 32-4 815 10 ‘E" 0.2 0.05 ‘ 0.08% Rhenium 82.3 82.3 i v0.2 0.05 0.5% Indium 82.6 82.5 F" 0.2 0.05 0.08% Zinc 82.2 82.2 j 0.2 0.05 0.5% Thallium 82.3 82.3 G" 0.2 0.05 0.08% Cadmium 82.2 82.3 k 0.2 0.05 0.5% Germanium 82.5 82.6 H" 0.2 0.05 0.08% Gallium 82.4 82.4 1 0.2 0.05 0.5% Tin 82.6 82.5 ‘ l" 0.2 0.05 0.08% Indium 82.3 82.4 m 0.2 0.05 0.5% Thorium “32x3 _ 823 J" 0.2 0.05 0.08% Thallium 82.1 82.5 n 0.2 Q05 (15% Cerium 323 321 15 K" 0.2 0.05 0.08% Germanium 82.5 ‘82.5

0 0.2 0.05 0.5% Samarium ‘82.3 82.3 0'2 0505 ‘108% l . 8L: p 0.2 0.05 0.5% Lanthanum 82.2 82.3 ,, 0'2 0105 008% °."“"‘ 82' ' i . . - N 0.2 0.05 0.08% cerium 82.3 82.3

q 0.2 0.05 0.5% Titanium 82.3 82.4 .. . . . o 0.2 0.05 0.08% Samarium 82.4 82.5

r 0.2 0.05 0.5% Zirconium 82.4 82.3 PM 02 0'05 008% Lamhanum 82A 822

‘ ' 20 Q" 0.2 0.05 0.08% Titanium 82.4 82.2 " VR" _, 0.2 0.05 0.08% Zirconium ‘82.5 p 82.2

EXAMPLE 1A

This example is given for comparison‘ and is not TABLE IV bis within the scope of this invention. Example 1 is re- ' 1 Recycle peated by using a catalyst containing 0.25% of platinum 25 CATALYST " Yield ‘ gas (one single metal element), a catalyst containing 0.20% % by weigh‘ % (35+ % H2 of platinum and 0.05% of rhodium, and althird one % P‘ % Os %add“‘°"a1me‘a] by we‘gh‘ by "1°12

containing 0.20% of platinum and 0.05% of osmium. 3"’ 88% 38: 3-3331 flhflogléum 2;; gig - . _ ' . . . 0 o y enum . .

_ Each of these catalysts contalns about’ 1.14% of chlo 30 c” . 0.2 005 008% Tungsten 82A 81 4 flne- ' 3 d" 0.2 0.05 0.08% Manganese 82.4 82.1 ‘

Table II A reports, for these three catalysts as used, ' 8% 8.82 8.82:: ghenium . ' ~ _- ' . . . 0 inc . .

the C5+ yield and the 70 hydrogen contained in the g,. 01 (ms 008% cadmium 82:2 821 recyle gas when the desired octane number has been h" 0.2 0.05 0.08% Gallium 82.4 82.4 reache¢ ' ' ' ‘ ' ' 35 i" 0.2 0.05 0.08% Indium 82.3 82.4

. j" 0.2 0.05 0.08% Thallium 82.1 82.4 ‘It. may be observed that, when using a. catalyst con- k.. M 005 008% Germanium 822 824

taming only platinum, or even when using a catalyst l" 0.2 0.05 v 0.08% Tin 82.4 82.5 containing only platinum and rhodium or osmium, the O-Z (105 093% Thq?um 82-4 325

. M b t t. 11 1 th th bt . d .th n 0.2 0.05 0.08% Cerium 82.3 82.3 yie s are su s an la y ower an ose 0 mm wi 40 0.. 0.2 005 O_o8% Samarium 82A 823 catalysts A—R and a-r as shown in Tables I and II. p" 0.2 0.05 0.08% Lanthanum 82.3 82.2

q" 0.2 0.05 0.08% Titanium 82.3 82.1 TABLE II A r" 0.2 0.05 0.08% Zirconium 82.4 82.1

‘ _Recycle gas ‘

‘ Yield C5+ % H3 CATALYST (b. w.) by mole 45 EXAMPLE 3 .

015% '1" 81-3 _ 81-6 The production of gasoline of very high octane num

328;‘ g‘; 332% :1‘ ber obliges to operate under very severe conditions ‘ 6 t’ ' % 5 ’ ' which could be hardly supported by the catalysts em

. 5o ployed up It; day. Thehpresenlt example scliows that it is ‘ , uite ossi e to use t e cata sts accor in to t e in

EXAMPLE 2 q p y g

‘Example 1 is repeated while using catalysts A'-R’, a’-r', A”-R" and-a"-r" identical to catalysts A-'-R ‘and a-r, except that each of the catalysts A'~R’ and a’-r’ contains 0.004% of the third‘metal element and each of the catalysts A"—R" and a"—r" contains 0.08% ‘of the third metal element. All catalysts contain 1.14% of chlorine. " I

Catalysts A'—R' and a'~r' have given in veach case practically the same ‘results as the catalyst of Table II A containing 0.20% of platinum and 0.05%‘ of rhodium or osmium: catalysts A’—R’ and a’—r’ have'an insuf?cient content of the third metal. of group VIII. The results obtained with catalysts A"—R" and a"—r" are given in Tables IV and IV bis. They are substantially the same as. those obtained in Tablesl and II: ~

55

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65

vention, even in particularly ‘severe conditions, in view of obtaining gasoline of very high octane number. I The charge of Example 1 is treated in view of pro

ducing gasoline of 103 clear octane number. Catalysts A to R and a-r are used and compared to rhodium or osmium free catalysts Al-Rl. The other properties of the catalysts A1—R1 are those of the catalysts A—R and a-r employed in Example 1. The content of metal ele ments is only slightly modi?ed, so that the total content of metal elements is identical ‘for catalysts A1—R1 and catalysts A—R and a-r. Each of these catalysts contains 1.14% of chlorine. '

The experimental conditions are as follows:

Pressure 1 i‘ ' V ‘ 10 bars

Temperature . i 530°- C.

l-lz/hydrocarbons molar ratio 8

4,401,557; 11

-'continu,ed Naphtha weight/catalyst weight/hour 1.65

Table V reports the C5+ yield ‘and the‘ hydrogen content of the recycle‘ gas, after 200 hours. By way of comparison, when operating under the same conditions with a catalyst containing 0.2% of platinum and 0.05% of rhodium, the yield of C5+ is 75.1 by weight and the molar hydrogen content is 74.8%; again, by way of comparison, when operating under the same conditions with a catalyst containing 0.2% of platinum and 0.05% of osmium, the C5+ yield is,75 by weight and the molar hydrogen content is 74.6. » . l ’

TABLE ‘V -, CATALYST Yield Recycle % by weight _, ' % C5 gas

% additional by % H2 % Pt % Rh 05 metal 7 weight by mole

0.2 0.05 _ 0.5 Chromium‘ ‘ ' 79.4 78.5

a 0.2 -— 0.05 0.5 Chromium 79.3 78.5

A1 0.25 - _- 0.5 Chromium 77.4 77.8

B ~ 0.2 0.05 "‘- 0.5 Molybdenum 79.3 78.4'

b 0.2 - 0.05 0.5 Molybdenum ,. 79.4 78.3

B1 0.25 _- 0.5 Molybdenum 77.4 77.6

C 0.2 0.05 — 0.5 Tungsten 79.5 78.6 c 0.2 _' 0.05 0.5'Tungsten 79.3 78.3 C1 ‘ 0.25 —— — 0.5 Tungsten 77.6 77.7

0.2 0.05 — 0.5 Manganese 79.6 78.8 d 0.2 — 0.05 0.5 Manganese 79.4 78.7 D1 _ " 0.25 — — 0.5 Manganese 77.8 78.5

E 0.2 0.05 — 0.5 Rhenium 79.4 n 78.8

e 0.2 -_ " 0.05 0.5 Rhenium 79.4 78.7

E1 0.25 - _ 0.5 Rhe‘nium v77.5 78.0

F 0.2 0.05 _ 05 Zinc 79.4 78.5

r ‘0.2 — 0.05 0.5 Zinc I 79.5 78.5

F] 0.25 _ _ 0.5 Zinc 77.7 ' 78.2

G 0.2 0.05 - 0.5 Cadmium , 79.1 78.5

g 0.2 __ 0.05 0.5 Cadmium 79.3 ,78.3 G1 0.25 - __ 0.5 Cadmium _ 77.5 77.9 '

0.2 0.05 - 0.5 Gallium 79.8 78.8

h 0.2 _ 0.05 0.5 Gallium 79.6 78.7

1-11 0.25 __ _ 0.5 Gallium 77.7 77.9 1 0.2 0.05 _ 0.5 Indium 79.4 ' 78.7

1 0.2 _ ' ‘0.05 0:5 Indium" 79.4 78.6"

11 0.25 _ _ 0.5 Indium 77.6 78.0

J 0.2 0.05 _ 0.5 Thallium 79.3 78.6 _| 0.2 _ 0.05 0.5 Thallium 79.4 78.5

J1 0.25 __‘ 1, 0.5Thal1iurn , , 77.3, I.‘ 77.5 K _ 0.2 0.05 — ' 0.5 Germanium 79.4 78.7 k ‘0'2 _‘ ' 0.05 0.5 Germanium 79.4 78.6 ' K1 0.25‘ -_ _ ‘0.5 Germanium - 77.9 78.0 '

L 0.2 0.05 _‘ 0.5'Tin 79.5: * 78.7

1 1 0.2 - 0.05 0.5 Tin 79.3 *- 78.6

Ll ‘0.25 _ . -._ 0.5 Tin . 77.7 78.1

M 0.2 _ 0.05 . - _.'0.5 Thorium , I ‘ 79.4 “78.6

m 0.2 - " 0.05 0.5 Thorium] ’ ' 79.4 ' 7814,

M1 0.25 _ - ' - _ 0.5 Thorium - ' 77.6 77.6

N ‘ 0.27‘- '0.05 I - 0.5 Cerium ' I 79.8 ' 78.7 -

n 0.2 _ 0.05 0.5 Cerium » 79.4 . 786

N1 025 _ . . _ 0.5 Cerium 77,5. 77.5

0.2 ‘0.05 — 0.5 Samarium 79.6. 78.6 o . 0.2 _ 0.05 0.5 Samarium V 79.5 78.6

01 0.25 - - _' 0.5 Samarium 77.5 77.4

P 0.2 0.05 ’— 0.5 Lanthanum' ‘79.5 1 78.5 -

p 0.2 — 0.05 0.5 Lanthanum 79.4 78.5

P] 0.25 —— — 0.5 Lanthanum .77.5 77.4

Q 0.2 0.05 — 0.5 Titanium I 79.4 .- 78.5

0.2 r- 0.05 0.5 Titanium I 79.3 _, 78.5 Ql 0.25 — — 0.5 Titanium ' 77.5 ' 78.0

R 0.2 0.05 _ 0.5 Zirconium 79.4 78.5

r 0.2 ‘‘ 0.05"O.‘5'Zirconium 79.3 78.5 ‘

R1 0.25‘ - - 0.5 Zirconium 77.6 78.0

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. 12

EXAMPLE 4

Example 1 is repeated by using catalyst D1 of Exam ple 3 containing neither rhodium nor osmium. The yield of C5+ and the % hydrogen contained in

the recycle gas when the desired octane number (96.2) has been obtained are given in Table VI.

TABLE VI

CATALYST % by weight YIELD RECYCLE GAS % of additional % C5+ % H2

% Pt metal (b. w.) by‘grnole

D] 0.25 0.5 Manganese 82.0 82.4

Catalyst D1 thus yields results only slightly lower than those obtained by using catalysts D and (1. But the advantage of the catalysts according to the invention is mainly their very substantially increased life time, as compared to that of the catalysts employed up to day.

Table VII thus shows that at mid-run, by using cata lyst D1, the yield of C5+ and the % hydrogen content of the recycle gas are respectively lower than the yield of C5+ and the %'hydrogen content of the recycle gas, as obtained when using ‘catalyst D and d. Mid-run time depends on the catalyst; it is the higher as the catalyst is more stable; -it is, with only a few hours difference, about 560 hours .for catalysts D and d and only about 380 hours for catalyst D1. For guidance, midirun time is about 410 hours for a catalyst containing 0.2% of plati num and 0.05% of rhodium and 415 hours for a catalyst containing‘ 0.2% of platinum and 0.05% of osmium.

TABLE VII

RE vCYCLE GAS

YIELD ~ % 1-12 ‘ % b. w. % C5+ mid-run

CATALYST % of addi- mid-run , I I (in

% Pt % Rh % Os tional metal (b. w.) _. moles)

D 0.20 0.05 — 0.5 Manganese 82.1 , 82.1

d . 0.20 - 0.05 0.5 Manganese 82.2 82.2

D1 0.25 -— " — 0.5 Manganese 81.4 , .- 81.6

Although catalysts D], D" and d" cannot be perfectly compared since catalyst D1 has not the same total con tent of metal elements as the catalysts D" and d", it must be noted that by using catalysts D" and d" conforming to the invention and containing 0.2% of platinum, 0.05% of rhodium (catalyst D”) and 0.05% of osmium (catalyst d”) and relatively low amounts of manganese, the results obtained in Tables IV and IV bis are slightly higher than those obtained in Table VI by using ‘catalyst D1 which does not conform to the invention and con tains 0.25% of platinum and 0.5% of manganese with out rhodium or osmium. Above all, as shown hereinbe fore, the advantage of the catalysts conforming to the invention mainly lies in their very long life time. Thus, by comparing, on the one hand, the results obtained with catalyst D1 at mid-run in Table VII and, on the other hand, the results obtained with catalysts D" and d_"_ at mid-run in Table VIII, it clearly appears that the C57‘ yield and the % hydrogenof the recycle gas are substantially better when using catalysts D" and d", thus showing superiority of catalysts such as D" and d" with respect to a catalyst such @8131. Further, the mid run time of about 530 hour'sfwhen'using catalysts D”

13* and d", is far longer than that‘ observed with ‘catalyst D1, i.e. about 380 hours. " ' '7 i

TABLE VIII. , . _ TABLE 1x . _

- ‘ . ' Rli- Toluene/sv

, _> _ . , CYCLE ‘ Alight CATALYST‘ YIELD GAS ‘v I , hydro‘,

% by weight “% C5+ % H2 ' % % ‘ carbohs ' % of addi_ inidqun midqun CATA- % % % Lights Toluene (molar

% pt % Ru % 05 “(mar meta} (b_ w.) (b. w.) LY‘ST " '% Pt Rh _ Os Mn (moles) I lights ratio)

D" 0.2 ODS _ (103 31,6 81.7 '11 10 s 0.35 0.02 - 0.5 35.0 25.0 "01.714 ‘ v ‘ Manganese ‘ ‘ S1‘- ' 0.35 0.02 _ _ 40.3 24.1 0.598 P‘ '

a" 0.2 - 0.05 . 0.08 81.7 ' 81.0 T 0-35 —— 0-02 0~5 351 24-8 0.70m.»

Manganese , . ‘r, 0.35 - 0.02 — 40.5 24.1 0.595.v

'r ‘ i ‘ ~ 15 This ‘Table shows that introducing manganese sub“

EXAMPLE 5,. ,

Four catalysts‘S, S1,’ T and T1 are prepared; their speci?c ‘surface is 230 m2/ g, their pore volume 54 00/ g and their chlorine content 1.14%.’ V i ‘ v “

These catalysts were prepared by using alumina of 20 240 mZ/g speci?c surface and 59'cc/g pore volume. Catalyst S has been prepared by adding to 100 g of alumina, 100 vcc of an ‘aqueous solution of: " 1.90 g concentrated HCl (d£l.l9) 14 g of an aqueous solution of chloroplatinic acid of 25 2.5% b.w. Pt content ' ‘ ‘ '

0.8 g of an aqueous solution of rhodium trichloride of 2‘.5%,b.w. rhodium content, and i i

2.30 g of manganese nitrate. I _ ,

The components were contacted for S'khours, ?ltered, dried for 1 hour at 100° C., then roasted at530° C7 in dryv air (dried with activated alumina)‘ and ?nally reduced in a stream of dry hydrogen (activated alumina) for 2

30

hours at 450° C. The resulting catalyst contains, with 35 respect to alumina: , ' '

0.35% of platinum 0.02% of rhodium 0.50% of manganese 1.14% of chlorine. v g _ 40 Catalyst T was prepared..according to the same

method, except that’ rhodium was substituted with os mium (as an osmic. acid solution of12.:50% by b_.,w. ,os mium content’). ‘ v . t

The resulting catalyst contains: f, “ ' i 45 0.35% of platinum .. 0.02% of osmium 0.50% of manganese , .,~ . .

1.14% of chlorine. ,r. . v ‘

‘Catalysts S1 and T1 were alsoprepared according to 50* the same method,,except that they are free .of manga. nese. Catalysts S and T1 contain 1.14%: of chlorine. These four catalysts were tested in a n-heptane test. The operation is so conducted as to obtain the same conver sion with each of the catalysts S, 8], T1 andiT'l. Th 55 experimental conditions are as follows: <

pressure: 20 bars , ._ " 1" ‘ ‘

Hz/HC molar ratio: 5 > - - r 1,

weight of naphtha/ weight of catalyst/hour: v3. The reactor inlet temperature is '490":.-C:i29 C. 60 It is so selected ‘for each catalyst that the‘same con-. .

version is obtained with ‘each of the two catalysts (88% ' in eachca‘se)‘. 'f'i. ‘ =-‘ 1' "1

Table IX' summarizes for the catalysts‘ S, S1, T'and T1: the molar yield' of toluene, the amount of-lightthydro- 65 carbons produced and they ‘ratio toluene/light hydrocar bons which characterize‘ithe selectivity of the catalyst (by light hydrocarbons, we mean the C1—C4“cut). The '

4,401,557“ 14 highe'rrtheitoluene/light hydrocarbons'ratio, the better the 'selectivity‘of the catalyst. ‘ ‘ ‘ ' " "

stantially improves the selectivity of the resulting cata‘ lyst. -In the same manner, adding ‘one or more‘ of the other elements according to the invention improves the‘ ' behavior‘ of the catalyst. l

EXAMPLE 6

It could be deduced from example 5 that the better‘ > results obtained with catalysts S and T, as compared with catalysts S1 and T1, are attributable to the mere additiori of manganese to the catalysts S and T with increase of the total metal content. In fact, when com paring in Table X (n-‘heptane test under the same‘ oper ating conditions as for example 5) the results‘ obtained with ‘catalysts S and T and with catalysts S2, S3, T2 and T3 (series S contains rhodium and series T contains osmium) which‘iall have the same total content of metal elements, except that catalysts S2, S3, T2 and Tj'aré'free‘ of manganese, it is foundthat catalysts S and T give’ the best results, the conversion being 88%‘wit‘h each catal lyst.‘ Catalysts 5;, Sit‘, T2 and T3 have been prepared as described for catalysts S1 and T1. Their metal content’is giv'en’in Table X and their chlorine content isllp.l4%.

TABLE x ‘ ‘ Tolueife/

> 1 light: 1 l

‘.Lhydm . % , , carbons

CATA- % %> % Lights Toluene (molar ' LYST % Pt ' Rh Os Mn moles lights ‘ ratio)‘

S 0.35 0.02 — 0.5 35.0 25.0‘ 0.714. S; 0.35 0.07 ' 4 0 40.3 24.0 0.595 S3 0.40 0.02T — 0 40.2 24.0 5111-‘ 0.597'7" T 0.35 —— 0.02 0.5 35.2 24.9 r 0.707. .

T; 0.35 —- 0.07 0 40.4 24. 1 0.596 T3 .040 I — 0.02 , 0 40.3 24.2 0.600

It appears from these examples that the preferred‘ additional metals are essentially: tungsten, manganese, rhenium, gallium, germanium, tin, thorium, cerium and samarium. ‘ " '

What we claim: ' a

1; A reforming process which comprises contacting a hydrocarbon fraction under reforming conditions in- the presence of a catalyst containing a carrier and, by weight with respect to the catalyst carrier, (a) 0.005—l% of platinum, (b) 0.005—l% of rhodium or osmium; (c) 0.005~5% of an additional metal selected from the group consisting of chromium, tungsten, molybdenum, manganese, rhenium, gallium, indium, thallium, tho rium," cerium, samarium, lanthanum, zinc, cadmium, titanium and zirconium, ‘and (d) 01-10% of halogen.

2. A process according to claim 1, wherein the cata lyst carrier is alumina.

4,401, 5.57 15

3. A process according to claim 2, wherein the con tent of additional metal within the catalyst is 0.0l—4%. by weight of the catalyst carrier.

4. A process according to claim 2, wherein the con tent of additional metal Within the catalyst is 0.05—3% by weight of the catalyst carrier.

5. A process according to claim 1, wherein the halo , gen of the catalyst is chlorine.

6. A new catalyst comprising alumina and, by weight with respect to alumina, (a) 0.005-1% of platinum, (b) 0.005-1% of rhodium or osmium, (c) 0.05—3% of an additional metal selected from the group consisting of chromium, tungsten, molybdenum, manganese, rhe nium, gallium, indium, thallium, samarium, zinc, cad mium, titanium and zirconium, and (d) 0.1—l0% of halo gen. -.

7. A process according to claim 3, wherein the addi tional metal is tungsten. >

8. A process according to claim 3, wherein the addi tional metal is manganese.

9. A process according to claim 3, wherein the addi tional metal is rhenium. .

10. A process according to claim 3, wherein the addi tional metal is gallium.

11. A process according to claim 3, wherein the addie tional metal is thorium.

12. A process according to claim 3, wherein the addi tional metal is cerium.

13. A process according to claim 3, wherein the addi tional metal is samarium.

14. A catalyst according to claim '6, wherein said additional metal is manganese or rhenium.

15. A process according to claim 1, wherein the addi tional metal is manganese or rhenium.

16. A process according to claim 1, wherein said additional metal is manganese, rhenium or tungsten.

17. A process according to claim 1, wherein said additional metal is manganese, rhenium, tungsten or gallium.

18. A process according to claim 1, wherein the addi tional metal is manganese, rhenium, tungsten, gallium, or thorium.

19. A process according to claim 1, wherein the addi tional metal is manganese, rhenium, tungsten, gallium, thorium or cerium. ' '

20. A process according to claim 1, wherein the addi tional metal is manganese, rhenium, tungsten, gallium, thorium, cerium or samarium.

21. A process according to claim 1, wherein the addi tional metal is manganese, rhenium or gallium.

22. A process according to claim 1, wherein the addi tional metal is manganese, rhenium or thorium.

23: A process according to claim 1, wherein the addi tional metal is manganese, rhenium or cerium.

24. A process according to claim 1, wherein the addi tional metal is manganese, rhenium or samarium.

25. A reforming process which comprises contacting a hydrocarbon fraction at reforming conditions with a catalyst comprising a catalyst carrier material contain ing, by weight percent based on the carrier,

(a) 0.005-1% platinum, > (b) 0.005-1% rhodium, (c) 0.005-5% indium, and ((1) 01-10% halogen. 26. A catalyst comprising a carrier material contain

ing, by weight percent based on the carrier, (at) 0.005—l% platinum, (b) 0.005~l% rhodium,

5

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45

50

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65

.16 (c) 0.005-5% indium, and (d) 0.l—l0% halogen. 27. A reforming process which comprises contacting

a hydrocarbon fraction under reforming conditions in the presence of a catalyst containing a carrier and, by weight with respect to the catalyst carrier, (a) 0.005-1% of platinum, (b) 0.005-1% of rhodium or osmium, (c) 0.005-5% of an additional metal selected from the group consisting of chromium, tungsten, molybdenum, manganese, gallium, indium, thallium, thorium, cerium, samarium, lanthanum, zinc, cadmium, titanium and zir conium, and ((1) 01-10% of halogen.

28. A process according to claim 27, wherein the catalyst carrier is alumina.

29. A process according to claim 28, wherein the content of additional metal within the catalyst is 0.0l—4% by weight of the catalyst carrier.

30. A process according to claim 28, wherein the content of additional metal within the catalyst is 0.05_—3% by weight of the catalyst carrier.

31.. A process according to claim 27, wherein the halogen of the catalyst is chlorine.

32. A new catalyst comprising alumina and, by weight with respect to alumina, (a) 0.005-1% of plati num, (b) 0.005-1% of rhodium or osmium, (c) 0.05—3% of an additional metal selected from the group consist ing of chromium, tungsten, molybdenum, manganese, gallium, indium, thallium, samarium, zinc, cadmium, titanium and zirconium, and (d) 01-10% of halogen.

33. A process according to claim 29, wherein the additional metal is tungsten.

34. A process according to claim 29, wherein the additional metal is manganese.

35. A process according to claim 29, additional metal is gallium.

36. A process according to claim 29, additional metal is thorium.

37. A process according to claim 29, additional metal is cerium.

38. A process according to claim 29, wherein the additional metal is samarium.

39. A reforming process which comprises contacting a hydrocarbon fraction at reforming conditions with a catalyst comprising a catalyst carrier material contain ing, by weight based on the carrier,

(a) 0.005—1% platinum, (b) 0.005-1% rhodium, (c) 0.005~5% gallium, and (d) 0.140% halogen. 40. A catalyst comprising a carrier material contain

ing, by weight percent based on the carrier, (a) 0.005~l% platinum, (b) 0.005-1% rhodium, (c) 0.005-5% gallium, and (d) 01-10% halogen. 41. A process for reforming a hydrocarbon fraction

which comprises contacting the hydrocarbon fraction with hydrogen at reforming conditions with a catalytic composite comprising a porous carrier material contain ing, on an elemental basis, about 0.005 to about 1 wt. % platinum, about 0.005 to about 1 wt. % rhodium, about 0.005 to about 5 wt. % rhenium and about 0.2 to about 5 wt. % halogen, wherein the metals have been incorpo rated with the carrier by impregnation of the carrier with one or more aqueous solutions of the metal salts, and further wherein the impregnated carrier has been subjected to reduction with hydrogen for 2 hours at a temperature of 450° C. '

wherein the

wherein the

wherein the

17 4,401,557 42. A catalytic composite comprising a porous carrier -.

material containing, on an elemental basis, about 0.005 to about 1 wt. % platinum, about 0.005 to about 1 wt. % rhodium, about 0.005 to about 5 wt. % rhenium, and .

18 tion of the carrier with one or more aqueous solutions of the metal salts, and further wherein the impregnated carrier has been subjected to reduction with hydrogen

about 0.2 to about 5 wt. % halogen, wherein the metals 5 for 2 hours at? lempm'amm of 450° c-i have been incorporated with the carrier by impregna

I5

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