HYDROCARBON CONVERSION PROCESS

ΐ

the present invention relates to a method for converting hydrocarbon materials. More particularly, it relates to a catalytic process isomerisation and acyclic saturated alicyclic hydrocarbon.

Are known numerous: hydrocarbon conversion processes involving the use of catalysts metal halide. For example, the Patent of the United States of America ° 3,201 484 U sign that the niobium pentafluoride and tantalum pentafluoride may be used in connection with the hydrofluoric acid for the isomerization of hexane. Oe patent also indicates a catalyst based on niobium or tantalum is less than acid catalyst hexafluorantimonique. patent of the United States of America U ° 3,617 516 also hexafluorantimonique sign that the acid is a catalyst effective for isomerizing, the patents of the United States of America.

K° 2 6 83 763 ÎT and° 2 683 764 describe the use of tantalum pentafluoride or niobium pentafluoride in association with the hydrofluoric acid for refining hydrocarbon oils, or to activate the disproportionation of aromatics to alkyl substituents. The latter two patents also indicates that the systems/ TaP HE and ^ ^ HP/ ÎIbP are potent isomerisation catalysts, alkylation, cracking and other reactions. Finally, Eairbrother Collaborators and, in the "Journal of the Chemical Society", pages 3051-3056 ( 1951 ), indicate that the halides niobium and tantalum, used in conjunction, catalyze reactions of the type of Eriedel -Crafts.

It has now been found, and this is the object of the present invention, that a mixed catalyst containing metal halide hard to be reduced, preferably a metal fluoride, in combination with at least one molar equivalent, preferably a molar excess of a gas halide, active 1 ' hydroisomerization of alicyclic hydrocarbons and saturated acyclic, the catalyst of the invention has a limited solubility in hydrocarbons and it is not deactivated by contact with hydrogen at temperatures above about 25 °C. Furthermore, the catalyst is not deactivated when used to promote 1 ' hydroisomerization of charge carrying amounts of unsaturated compounds, sulfur compounds and/or benzene which, normally, poison catalysts of the type Priedel -Crafts.

3 The catalyst.' invention is effective for the transformation and alicyclic acyclic aliphatic hydrocarbons having at least four carbon atoms in a product enriched with one isomer of these hydrocarbons. For example, acyclic hydrocarbons having at least four carbon atoms, i.e. paraffinechaîne straight or branched having about 4 TO 10 carbon atoms, preferably about 4 TO 8 carbon atoms, branched are transformed into products of higher octane numbers. Moreover,

alicyclic hydrocarbons (naphthenes) having at least about 5 carbon atoms, for example about 5 TO 50 carbon atoms and preferably 5 TO 15 carbon atoms, can be transformed into their isomers by contact with hydrogen in the presence of the catalyst of the invention. Mixtures of cyclic hydrocarbons and alicyclic can be used as treated in the method.

In a typical industrial operation, a paraffin stream containing mixtures of various types of open-chain paraffin is used as feed.

one of the remarkable features of the catalyst of the invention is that it can be used in the presence of quantities of substances which normally poison conventional catalysts of Priedel - Orafts. For example, the treated feedstock may contain amounts of unsaturated organic compounds (olefins and acetylenes), benzene or sulfur compounds normally that would destroy the activity of a conventional catalyst of Priedel - Orafts. Therefore, the load does not need to be purified by removing of the above subject matters, before being used. For example, the feed may contain substantially any benzene (or other aromatic hydrocarbons) or olefinic compounds without affecting significantly the activity of the catalyst, provided that sufficient amounts of hydrogen are present in the reaction zone ' to saturate aromatic hydrocarbons and/or olefin. A substantially any amount of sulfurized materials may also be tolerated, provided that the molar ratio of the sulfur compounds the metal halide does not substantially exceed about 1:1. Examples of loads that may be treated with the catalyst of the invention contain about 0,001 TO 10 , in particular 0,01 TO 2,0 fi by weight of unsaturated components, 0,01 TO 10 , in particular 0,075 TO 5,0 fi > by weight of benzene or other aromatic compounds and 1 TO 10 000 , in particular 50 TO 500 parts per million by weight of sulfur compounds.

hydrogen used in the isomerization may be provided by any suitable. For example, in 3 a refinery operation, hydrogen used may be a crude or impure hydrogen stream as that obtained in the process of reforming of naphtha, again, due to the ability of the catalyst of the present invention to tolerate sulfur poisons, the hydrogen does not need to be purified by removing sulfur prior to use. Alternatively, hydrogen can be generated in situ by introducing hydrogen-eliminating compounds in the reaction zone during the reaction. Examples of valuable compounds releasing hydrogen include materials such as decalin, tetralin, the miéthylcyclohexane, andc. A particularly preferred introducing elemental hydrogen in the reaction zone.

the hydroisomerization reaction may be conducted by weight, i.e. in the absence of any solvent, or it may be carried out in the presence of a solvent or diluent. The solvents or diluents include fluorinated paraffins, sulfolane, sulphur dioxide, chloride or sulfuryl fluoride, fluorinated acids and/or acid anhydrides, the gas hydrofluoric, andc. The hydrofluoric the reaction diluent gas is preferred when the metal portion of the catalyst is a metal fluoride.

Hydrofluoric When the gas is the diluent, in the case of catalysts consisting of metal chlorides or bromides, becomes finely divided producing an exchange reaction which converts the metal metal fluoride. When using a solvent or diluent, their amount must be sufficient to maintain the viscosity of the reaction mixture to the desired value. For example, using about 0,25 TO 50 and preferably about 1 TO 20 volumes of solvent or diluent per volume of hydrocarbon feed.

As stated above, the hydroisomerization catalyst is composed of a metal halide hard to be reduced in association with a halide gas. The interest in metal halides used include fluorides, bromides and chlorides

gallium, tin, lead, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.

rare, as well as trans-lived metals, in particular uranium, neodymium, and aluminum chlorides and bromides.

The preferred components of the catalyst metal halides are halides of tantalum and niobium, preferably tantalum pentafluoride, the niobium pentafluoride and mixtures thereof.

the second component of the catalyst is a halide gas. The materials interest include

the hydrogen bromide gas, the gas the gas hydrochloric and hydrofluoric. To avoid exchange reactions, it is desirable that the halide gas halide does not cause exchange reactions with 1 ' metal halide used in the composition of the catalyst. For example, in the case of using the tantalum pentabromide. metal component, the gas halide preferred cocatalyst is used as the hydrogen bromide gas, because the halogen gas of hydrochloric and hydrofluoric are capable of exchanging with the bromine atoms tantalum bromide representing the metal component. The halide gas halide is advantageously is the same as that of the metal halide gas. the preferred halide used as a component of the catalyst is hydrofluoric the gas.

catalyst efficiency is directly proportional to the molar ratio of the halide metal halide gas entering the catalyst composition.

A at least equimolar amount of halide gas relative to the metal halide is to ' be present in the reaction zone, the ratio of the gas halide metal halide is advantageously at least equal to 2 ; 1 and, preferably at least about 5:1.-In the case of catalysts pentafluorides base tantalum and niobium, the provision of large molar excess hydrofluoric gas in the reaction zone was capable of improving the reaction rates. Depending upon the relative amounts of the components of the catalyst is used, the catalyst, in the absence of support, may be a homogeneous solution of halide gas and a metal halide or a mixture of metal halide and solid dissolved in the acid halide.

In addition to the case where fillers are used sulfurized, the amount of a metal halide of the catalyst in the reaction zone is not critical. For example, of.

amounts of about 0,001 TO 10 , and, preferably about 0,01 TO 5,0 parts by weight of halogénuresàétalliques are present in the reaction zone per part by weight of hydrocarbon reaction, when the load contains sulfur-containing impurities, it is desirable, if it is desired to operate the maximum activity of the catalyst, that a molar excess of the metal halide is present in the reaction zone relative to the amount of poison sulfide present in the reaction zone at each instant, sulfur and sulfur compounds likely form complexes with the metal halide used in the composition of the catalyst. A balance is established between the amount of complex formed sulfide and the amount of sulfur contained in the hydrocarbon phase. Therefore, all of the sulfur present does not react or complex with the metal halide used in the composition of the catalyst. Furthermore, the complex forming reaction appears to be reversibly in that the concentration of the sulfide complex or the reaction product is reduced when the catalyst contacts a-free filler sulfur.

As stated hereinbefore, the catalyst composition of the present invention is not impeded by the presence of benzene or other aromatic compounds, sulfur compounds or organic compounds irisaturés.

However, if it is desired to operate the maximum activity of the catalyst, fillers, diluents and leConstituants of the catalyst may be purified prior to use to remove water, nitrogen and/or nitrogen compounds such as amines or ammonia. The nitrogen compounds or compounds form stable complexes with the catalyst components, the presence of small amounts of water or of nitrogen, can be tolerated if the corresponding loss of catalyst or the drop of catalytic activity is acceptable. Preferably, the concentration of water or of the nitrogen compounds in the reaction zone should not exceed about 0,01 o/by weight and, preferably, about one part per million by weight on.

the basis of the total catalyst. A particularly preferred that the hydroisomerization reaction is conducted in the substantial absence of water and/or nitrogen compounds.

In conventional operation of refining, the treated feedstock, hydrogen and the solvent, if present, are mixed with the catalyst in a substantially liquid-phase operation, the contacting can be performed in more mixing zones connected in series. In this type of operation, the catalyst phase and the hydrocarbon phase are separated after the reaction and the product is isolated of the charge ^ ayani as reacted by procedures' distillation. Optionally, the metal halide, preferably a metal fluoride, used in the composition of the catalyst, can be fixed by impregnation on a porous support, inert (compared to the nic halogénhyd gas) such as an oxide réfractairqfluoré, the glass "Vycor" fluorinated, graphite, the supports based on polytetrafluoroethylene " Teflon ¹¹ such as "Chromosorb T" and " Fluoropak 80^K , and the load and halogenhydrique acid used as cocatalyst are guided over the metal halide attached to the base, or in liquid phase, or in the gas phase, or mixed phase. Alternatively, the halide acid and the metal halide constituting the catalyst can be fixed by impregnation on a support material HF resistant and the load can be passed over the catalyst. In a using a supported catalyst, the hourly space velocity of the reaction liquid (volume feed liquid per hour per volume of catalyst) is to be maintained at values below about 200 .

hydroisomerization reaction temperatures may vary from about 0 to 150°Cj preferably, is used temperatures of about to 100 °C 25-30. A particularly preferred conducting the reaction at a temperature between about 50 and 60 °C. In most cases, the process is carried out at a temperature of about 45 0 and 60°.

It has been found that the reaction rates of isomerization rise significantly with the reaction temperature. Also, undesirable waxy feeds a hydrocracking takes place at an increasing rate when high temperatures are employed, the precise temperature used in the reaction is to thereby allow a compromise entre' the advantage of increasing the speed of reaction and the deficit caused by the loss of load by processing hydrocracked low molecular weight.

the isomerization reaction is preferably carried out at a temperature sufficient to maintain the hydrocarbon feed and the catalyst substantially liquid-phase, pressure hydrogen partial pressures in the reaction zone may vary from to about 1.75 140 , preferably about 1,75 to 28 bar. the reaction zone typically contains. 0,05 TO 2,5 moles, preferably 0,05 to one mole of hydrogen per mole of molecular hydrccarnée load. Typical In a reaction system, the isomerization reaction may be conducted during periods of time that vary from about 0,5 TO 1500 and, preferably about k 500 1 min. Of course, the reaction time is related to the temperature and the process is performed for a sufficient period of time for forming a product enriched with an isomer of at least one of the hydrocarbon components of the load.

Reactions involving the use of catalysts based on a metal fluoride and ^ Æluorhydrique ga may be conducted in carbon steel containers, k condition without using excessive temperatures and maintain the reaction system under substantially anhydrous conditions. It is also possible to use a low carbon stainless steel (series 300) or the "Monel" for the embodiment of the apparatus.

The invention is illustrated by the following examples.

Unless explicitly specified otherwise, all percentages and all parts are expressed by weight.

Example 1

Is charged mixture in a molar proportion

80:20 of n-hexane (209 ml, 1.60 mol) and cyclohexane (43 ml, 0.40 mol) in a reactor Parr model 4521 alloy " Hastelloy C^u one liter capacity, equipped with an agitator. Is added into the reactor 55.2 g (0.2 mole) of tantalum pentafluoride. Reactor is removed from the protective case, closed, it creates a partial vacuum by means of a horn k water is introduced and 20 g (one mole) coming directly from a bottle k volume indicator. Thereafter in the reactor a gauge pressure hydrogen 7 bar (a hydrogen pressure of 2,94 k bar is about 0,1 mole of level i ^) and the reaction mixture is stirred at 600 rpm for one hour k 50 °C. A sample is removed from liquid k 50 °C by connecting the reactor one litre k a cylindrical test stainless steel 10 ml, held under vacuum, by opening their valves and forcing the liquid through a dip tube in the smallest container, by pressure difference. Is cooled 1 ¹ sample to- 70° 0 one aliquot is analyzed and on. a gas chromatography apparatus Model 1520 " Aerograph" column "DC 200" on " Chromo sorbP" (3.75 mm. x 915 cm) to 90 °C. L^, analysis shows the distribution of products and the conversion rate following indicated:

FREE 2 _AOE280A2AO>

The follows the operational mode of the example 1à the difference that the catalyst is prepared using 26 g hydrofluoric gas( 1,3 mole) and hydrogen under pressure of 1,75 bar, and the following are achieved in regards to the delivery of the products and the rate of:

transformation.

Distribution products Percent by surface based on the gas chromatography analysis

£ ai22L -As-Tr. Has. has _AOUNI167AO>. £<? am- tiQn

Iso-C ₆

n-Cg recovered

methylcyclopentane + cyclo-

hexane recovered

Percent by surface 80,98

6,52

10,59

Transformation Rate

l¹ normal hexane, fi 92,10

Compression ratio of transformation of the

cyclohexane 47,05

Oes 1 * results demonstrate that the catalyst of interest has 1*invention. A comparison of the results of the example 1 with those of the example 2 highlights that the getting the best rate of transformation of the hexane dimethylbutanes when raising the molar ratio HP/ TaP_r .

The results of the examples 1 and 2 demonstrate that large amounts of cyclohexane are hydrocracked open-chain products. Finally, the results show that the presence of relatively large quantities of cyclohexane in the reaction zone does not interfere with the catalyst.

EXAMPLE 5

By using the same reactor as in the example 1,

is charged a mixture to 9 0:10 n-hexane (255 ml, 1.80 mol) and cyclohexane (21.6 ml, 0.20 mol). The reactor is then charged with tantalum pentafluoride( 52,2 g, 0,2 mole). Is removed the reactor shroud, closed, it creates a partial vacuum by means of the water hose and gas is introduced hydrofluoric (21 g, 1,05 mole) by direct connection with a bottle having a volume indicator. Hydrogen is then introduced into the reactor in gauge pressure of 1.75 bar. Is heated to 50 °C the resulting mixture, in the stirring for three hours and a sample is obtained. The analysis by gas chromatography (see example 1 ) gives the following values in regards to the delivery of the products and the transformation rate.

Ethane

Eropane

Isobutane

Butane normal

Isopentane

Pentane normal

2 . 2 -dimethylbutane

2 . 3 -dimethylbut anei

2 - methylpentane J

3 ent- méthylp ane

Hexane normal

dope méthylcy ane

Cyclohexane

Total surface,

Percent by surface 0,13

0,44

1,17

0,27

0,84

0,12

42,93

33,10

11,53

6,82

0,42

... 2,2 5-

100,00

This experience demonstrates, by comparison with the results of 1 * example 2 , the effect of reducing the molar ratio of tantalum pentafluoride hydrofluoric at gas in the catalyst. In this specific case, a reaction time is three times longer required for ' efficiency like, * amounts are used when reduced HE.

EXAMPLE 4

For purposes of comparison, is carried out following experience, by substantially the same manner as in the example 3 ,* to the difference that is used 17 g of hydrogen chloride( 0,9 mole) and that the reaction is carried out in the absence of hydrogen. The values of distribution of products and transformation ratio obtained after a reaction time of one hour are the following:

TO

the results of the experiment demonstrate clearly the effect of the presence of hydrogen on the efficiency of the isomerization process.

A comparison of the results of that experience with those

qu_

example 3 / reveals the presence of hydrogen increases notableue

the conversion of the hexane reaction dimethylbutane which constitutes an advantageous product.

ΕΒΒΜΕΕΒ 5

This example illustrates the possible implementation of the method of the invention in the presence of poisongjtypique_AOUNI167AO> & u catalyst such as benzene.

Is loaded, in a reactor a liter, of the type described in the example 1 , 235 toi (1.80 mol) of n-hexane, 21,6 ml( 0,20 mole) of cyclohexane and 3,55 ml (0.04 mol) of benzene, to form a mixture of reactants and poison the catalyst in the molar ratio of 88 , 24 / 9 , 80 1.96/mole. Is added to the reactor 55.2 g (0.20 mole) of tantalum pentafluoride. Reactor is removed from the protective case, closed -, it creates a partial vacuum to the vacuum tube, and gas is introduced hydrofluoric (51 g, 2,5 mo3.es). Hydrogen is then introduced into the reactor in gauge pressure of 5,25 bar and the reaction mixture is stirred at 600 rpm during vine hour to 50 °C. The below the results that the obtained by that method. in regards to the delivery of the products and the transformation rate.

Ethane

Propane

Isobutane

Butane normal

Isopentane

Pentane normal

2 , 2 -dimethylbutane

2 , 5 -dimethylbutane n

2 ~ methylpentane J

3 ~ methylpentane

Hexane normal

Cyclopentane Méthy3.

Benzene

Cyclohexane

Total surface, fo.

0,05

0,27

1,08

0,25

0,46

0,07

43,20

32,27

10,87

6,82

0,75

0,20

3,78

100,04

Is that the iso ~ hexan. es hydroisomerized are obtained by a high yield despite the presence of benzene. Furthermore, the catalyst/HP allows ^ TaP saturate and/or hydrocracking the major portion of the benzene.

The following examples illustrate the use of mixtures of tantalum pentafluoride and niobium pentafluoride and the use of the single niobium pentafluoride, as catalysts for the conversion of hydrocarbons to mixture with hydrofluoric acid.

EXAMPLE 6

In according to the process of the example 3, is fed to the reactor 27,6 g( 0,1 mole) of tantalum pentafluoride and 18.8 g( 0,1 mole) of niobium pentafluoride.

Reactor is removed from the protective case, closed, it creates a partial vacuum to the water hose and 45 is introduced g (2.3 moles) hydrofluoric gas. Is introduced into the reactor 0,4 g( 0,2 mole) of hydrogen under pressure and the reaction mixture is stirred at 600 rpm for two hours at 50 °C. Following values are obtained with respect to the distribution of products and the transformation rate.

Ethane

Propane

Isobutane

Butane normal.

Isopentane

Pentane normal

2 , 2 -dimethylbutane

2 , 3 ^-dimethylbutane

2 - methylpentane J

Surface, jo

0,04

0,14

0,25

0,11

0,22

0,05

41,57

33,65'

3 -methylpentane 11,32

Hexane standards l 6.42 Méthylcyclopentane 1.02 Cyclohexane 5.22

Total surface, % 100,01

false surface transformation, j" Iso-Cg 86.54

n-Cg + 6.42 Méthylcyclopentane recovered cyclohexane

recovered 6.24

Compression ratio of transformation of n-hexane, $ 92.87

Rate ' transformation cyclohexane, $ 37.60

EXAMPLE 7

Is loaded, in the reactor described in the^l example 1, a mixture of 235 ml( 1,8 mole) of n-hexane, 2,6 ml( 0,2 mole) of cyclohexane and 8,8 ml (0.1 mole) benzene. Is then added into the reactor 37,6 g( 0,2 mole) of niobium pentafluoride. Reactor is removed from the protective case, closed, wine is creates partial vacuum to the vacuum extractor tool and 42 is added g (2.1 mol) fluorbydrique gas. L then is introduced^l pressurized hydrogen( 1,2 g, 0,7 mole) in the reactor and the reaction mixture is stirred at 600 rpm at 50 °C during 17 hours. Following values are obtained with respect to the distribution of products and the transformation rate.

The procedure is repeated 1*exemple 6 using a catalyst containing 5,52 g( 0,02 mole) of tantalum pentafluoride and 33,52 g (0.18 mol) of niobium pentafluoride.

Is added 55 g (2.7 moles) hydrofluoric and gas is fed to the reactor l * pressurized hydrogen( 0,2 g, 0,1 mole). Are the reaction mixture at 600 rpm during 6 hours to 50 °C. .0n obtains the following values, in regards to the delivery of the products and the transformation rate.

the following examples illustrate the practicability of the method of 1 * invention in the presence of various sulfur compounds poison on the catalyst.

FREE 9

The described procedure in 1*exemple 3, is fed to the reactor 3.61 g( 0,04 mole) of isobutylmercaptan, which is about 7000 parts per million sulfur. Is added to the reactor 55.2 g (0.20 mole) pentafluoride tantalei is removed from the reactor shield box, closed, a partial vacuum is formed to the water hose and is added 57 g (2.8 mol) fluorhydriqueà gas is introduced hydrogen in the reactor under superatmospheric pressure of about 5,25 bar and the reaction mixture is stirred at 600 rpm for one hour at 50 °C. The following results are obtained with respect to the distribution of products and the transformation rate eroism

Surface Distribution products" jo ethane 0,02

It should be note that yields of isomerization and hydroisomerization despite the presence of a sulfur compound poison on the catalyst ₀ EXAMPLE 10

In according to the procedure described in example 3, is fed to the reactor 2,48 g( 0,04 mole) of dimethyl sulfide, which is about 10 000 parts per million sulfur. Is introduced into the reactor 55.2 g (0.20 mole) of tantalum pentafluoride. Is removed from the reactor shield box, closed, is' thereby a partial vacuum using the vacuum extractor tool and 48 is introduced g (2.4 moles) hydrofluoric gas. The gauge pressure of about 3" 5 bar with hydrogen in the reactor and the reaction mixture is stirred at 600 rpm for 1 hour to 50 °C.0n obtains the. following results in regards to the delivery of the products and the transformation rate;

Transformation Jaux surface,

_AOE296A0AO> méthylcyciopentane + cyclohexane

recovered 6,14

transforming ratio of the n-hexane, io 92,43

transforming ratio of the cyclo-

hexane, Ÿ > 37,35

It should be noted that the * is to provide high yields of products isomerized despite the presence of large amounts d * a sulfur compound poison on the catalyst.

EXAMPLE 11

By using the described procedure in 1*exemple 3, a 3,33 g( 0,04 mole) thiophene, which is an amount d^l about 2 ^ by weight of the reactants. Is added to the reactor 55*2 g (0.2 mole) of tantalum pentafluoride; Furthermore, 52 is introduced g (2.6 moles) hydrofluoric gas. Thereafter in the reactor a gauge pressure d^t d * about hydrogen 5,25 bar and the reaction mixture is stirred at 600 rpm for 4 hours at 50 °C. The following results are obtained with respect to the distribution of products and the transformation rate:

Distribution products s Surface. % ethane propane 0.08 0.24 0.49 isobutané 1.63 normal butane isopentane 0.99 normal pentane 0.16 2 , 2 -dimethylbutane 43.96 2 , 3 -dimethylbutane 2 -methylpentane J\ 32,27 3 -methylpentane 11,21 normal hexane 6,22 methylcyclopentane 0.43 cyclohexane

iso-CL

Surface" f > 87,44

6,22

n-Cg recovered

méthylcyciopentane + cyclohexane. _AOE296A0AO> recovered 2,32 transforming ratio of the n-hexane, f 92,95 transforming ratio of the cyclohexane, fo 71,94 This example demonstrates that the catalysts used in the present invention are mostly insensitive to relatively large amounts of sulfur compounds poison conventional catalysts Eriedel -Crafts.

EXAMPLE! 12

1 * following example demonstrates that the catalyst of the present invention can be used in the ' of benzene and sulfur poisons.

The procedure 1*exemple 3, a 3,54 ml( 0,04 mol) of benzene and 0,073 ml (0,001 mol) of dimethyl sulfide. The reactor is then charged with 27,6 g( 0,1 mole) of tantalum pentafluoride and 18.8 g (0.1 mole) of niobium pentafluoride. Then " gas is introduced hydrofluoric (67 g, 3,2 moles) in the reactor. Thereafter in the reactor a pressure hydrogen( 0,6 g, 0,30 mole) and the reaction mixture is stirred at 600 rpm to 50 °C during 3 heuresi The following results are obtained in the distribution ' products and the transformation rate:

33,33

It should be noted that the simultaneous presence of typical poisons catalysts Eriedel -Crafts exerts substantially no influence on 1 * ability of the catalyst to activate a hydroisomerization reaction;

The following examples illustrate the practicability of the method of 1 invention in the presence of other toxic substances such as olefins, phenanthrene and 1 * hexaméthyfbenzène ^l ,

EXAMPLE 13

Is loaded in a reactor a liter of the type described in the example 1 , 235 ml (1.80 mol) of n-hexane and 10,4 ml (0.10 mole) of cis-2-pentene. Is introduced into the reactor 55.2 g (0.02 mole) of tantalum pentafluoride; reactor is removed from the protective case, closed, it creates a partial vacuum by means of the water hose and introducing gas hydrofluoric (34 g, 1.7 mol); then is introduced hydrogen under pressure in the reactor( 1,0 g, 0,5 mole) and the reaction mixture is stirred at 600 rpm to 50 °C.

during 4 hours; are obtained following résulvats in regards to the delivery of the products and the transformation rate, after the first hour of reaction:

transforming ratio of the cyclohexane, fo 58,51

It should be noted that the presence of the olefinic poison n * exerts a detrimental effect on the reaction of hydro-, isomerization of the present invention ₀

EXAMPLE! 14

Is loaded in a reactor a liter of the type described in the example 1 , 209 ml (1.60 g) of n-hexane, 45 ml( 0,40 mole) of cyclohexane and 7.13 g (0.04 mole) phenanthrene. Is introduced into the reactor 55,2 g( 0,2 mole) pentafluoride tantalei is removed from the reactor boîtede protection, closed, it creates a partial vacuum by means of a fluid jet pump and adding 55 g (2.8 mol) hydrofluoric gas. Is then introduced into the reactor of the pressurized hydrogen (2.6 g, 1.3 mol) and the reaction mixture is stirred at 600 rpm for 4.5 hours at 50 °C. After the first three hours of reaction, the following are achieved in regards to the delivery of the products and the. rate of transformation:

Ethane

Propane

Isobutane

Butane normal

Isopentane

Pentane normal

2 . 2 -dimethylbutane

2 . 3 - dimétbylbutane

2 - méthylpentsne

3 -methylpentane

Hexane normal

Méthylcyclopentane

Cyclohexane

Iso-C.

0,25

0,65

0,96

0,56

1.04

0,21

40,86

53,67

11,43

6,57

0,75

3.04

Surface jo 85,96

6,57

n-Cg recovered

Méthylcyclopentane + cyclohexane

recovered 3.79

Compression ratio of transformation of n-hexane, i° 91,62

II should be noted that the presence of phénan thrène does not harm the hydroisomerization reaction of the invention.

15 FREE

In according to the procedure described in example 14, but by replacing the phenanthrene by 6.5 g (0.04 mole) of hexamethylbenzene, . is removed from the reactor the shield box, closed, it creates a partial vacuum to the water hose and introducing gas then hydrofluoric (44 2,2 moles). Is then introduced into the reactor of the pressurized hydrogen( 1,8 g, 0,9 mole) and the reaction mixture is stirred at 600. rpm for 17 hr to 50 °C. The following results are obtained with respect to the distributed-

EXAMPLE 16

Is loaded, in a reactor Parr in "Hastelloy-O" die capacity of one litre, equipped with a stirrer, 250 light naphtha ml virgin " boiling atmospheric pressure between the room temperature and 81 °C, 0.20 Mole (55.2 g) of tantalum pentafluoride, 2,35 moles (47 g) hydrofluoric gas and 0.2 mole (0.4 g) hydrogen. Are the reaction mixture during 1 hour to 600 rpm at a temperature of 50 °C. Furthermore, a sample is obtained from the reaction mixture and subjected to tests is chromatographiqu._e The present invention provides a chromatography apparatus type Perkin Elmer 900, equipped with a column of "LC 200" of 915 cm x 0,254 mm. Is gas chromatography at an initial temperature of the column of -20°C and raising the temperature of the column at a rate of 4 °C per minute to a final temperature of 130 °C.

Analysis of the raw material and of the product formed is indicated on the following table eroism

From these results that the relative amounts of branched chain materials present in the product stream substantially increase from the levels present in the initial charge. For example, the concentration of isohutane, isopentane, 2 , 2 - diméthylhutane and 2 , 3 - diméthylhutane in the product increases relative to the corresponding level in the load, while the relative concentrations of straight-chain paraffins and branched chain

, 3 methylpentan-such as pentane normal , the 2 - methylpentane, l^I hexane, the/ normal heptane and normal in the product decrease relative to the amounts present in the feed. Finally, the concentration of the benzene in the product stream is reduced more than 50 f relative to the amount present in the initial charge.

EXAMPLE 17

Using the reactor 1*exemple 16, a test is performed to demonstrate 1 l * ability of the catalyst¹ The invention to activate 1 * Isomérisation of naphthenes lower molecular weight. Hans this assay, a 250 d * ml a typical product refinery boiling between 82 and 177 °C at atmospheric pressure, 0,20 mole( 55,2 g) tantalum pentafluoride, 1 , 9 ' mole (38 g) hydrofluoric and gas 0,15 mole (0.3 s) hydrogen. The content of the reactor is heated at a temperature of 25 °C and maintained this temperature for 2 hours. Are the reactor contents at 600 rpm. Analysis of the load and of the product, performed using a mass spectrometer model* 2 H 03 C dealer Consolidated Electrodynamics Corporation, is indicated on the following table eroism

Since the demonstrates 1*analyse, the amount of cyclopentanes present in the product stream is substantially less than the quantity in the feed. Instead the product stream s¹ cyclohexanes is enriched with respect to the load current.

EXEMPIE 18

By using the reactor 1 ' example 16, is carried two trials to demonstrate 1 * ability of the catalyst of the present invention to be isomerized mathyloyclopentone to cyclohexane. In each of the tests, is used as the filler equimolar amounts of benzene and methylcyclopentane.

In each test, the same catalyst is used containing 0,20 mole( 55,2 g) tantalum pentafluoride and 2,6 moles (52 g) hydrofluoric gas. In both tests, use is made of a hydrogen partial pressure of 3.5 bar, the test results are given below level i

highly active prevention transforming the méthylcyelopentane to cyclohexane, the ability of the catalyst to activate this reaction has a very great importance, because the catalyst can be used to enhance the charge circuits When introduced into hydroforming where it is desirable that. the amount of cyclohexane to the méthylcyelopentane is maximum. Furthermore, it should be found that the elevated levels of transformation are obtained in the presence of a large molar excess of benzene (relative to the catalyst). It is known as benzene, even in small amounts, a catalyst deactivates Eriedel -Crafts.