Process of hydrocarbon conversion.

AS AFRICAN AND MALAGASY

INDUSTRIAL PROPERTY

P. 887

Yaounde (Cameroon) Patent International Patent Classification: c10 no. 01295

Cmîp.i.

v->

31 December 1964 to 18 hr 36 requested Mn to ioio.a.m.p.i.

(G.P. no. 51,708) by french petroleum Institute, fuels and lubricants, residing in France.

Delivered 15 February 1969, published at Official ballot n° 4/5 of 1968. Priority: Patent application filed in France under the n^bone 894.174 894,321 and the 11 April 1962 and 12 April 1962.

A hydrocarbon conversion process. (Disclosure: Dr. Robert DUTRIAU, Dr. Robert BOSG and jeans-to-by Claude impediments.)

Refineries have generally excess

hydrocarbons, mainly paraffinic, bouil -

insulation in the range essences and/or naphthas, and

for example in the range 30 - 220 °c under pressure

atmospheric. These hydrocarbons have an index of an OC -

tan poor.

Further since, demand of hydrocarbons

light paraffinic, containing 3 or 4 atoms because -

bone Morphogenic, in particular branched type, increases without

ceases, the been required to transform the

essences and/or highly paraffinic naphtha in

light paraffinic hydrocarbons.

It should be however that the catalyst is particularly good -

as particularly active and that it has a good resistance to

the deactivation. It has been found that the conventional method

hydrocracking hydrocarbons heavier than the

naphthas could not be suitable and the catalysts

known hydrocracking naphthas or gasolines

were insufficiently active or désactivaient too

quickly.

The present invention provides a selective method of

conversion of hydrocarbons boiling in the range

gasoline and naphtha, particularly those

whose earactère paraffinic is acknowledged, hydro -

light paraffinic carbides, mainly c - c,

in particular branched type.

The method is distinguished from methods of hydrocra -

conventional quage by employing a catalyst préala -

blement treated by boron fluoride gas, in

particular conditions.

The method cousist essentially passing

hydrogen and hydrocarbons such as gasolines

and/or naphtha in a reaction zone - tale

a catalyst comprising simultaneously a olvement - Sub

port activity crumbly and PLA is a metal of group -

tINE-, said catalyst having been previously processed by

boron fluoride gas, in a dry atmosphere, to a

temperature of between 100 and 500" préfé - Cl

conference between 200 and 400 °c. The treatment by fluo -

boron fluoride is continued, for example, during

10 minutes to 24 hours, preferably 1 to 6 hours,

without these limits have been imperative. However, at -

below 15 min, the effect is relatively

low, while that with beyond 24 hours, continuing the

treatment is generally not economically justified.

Boron fluoride may be diluted in dry air or in a dry inert gas.

The conditions of the reaction of converting gasoline and/or naphthas include a temperature of 300 to 500 °c, preferably from 375 to 450 °g, and a pressure of 15 to 250 atmospheres, preferably 30 to 150 atmospheres.

The space velocity, defined as the volume hourly load passing through the unit catalyst volume, is generally between 0.2 and 6, and preferably between 0.5 and 2.

Hydrogen is generally agreed in the catalytic zone in an amount of 400 to 4,000 liters per liter of hydrocarbon feedstock, under normal conditions of temperature and pressure, without limits have been absolutely imperative SEA, the actual consumption of hydrogen reaching however that 50 per liter to 250 liters load in most cases.

The platinum group metal is preferably platinum itself, although it can also be used for example palladium or rhodium. The metal is typically used in an amount of 0.05 to 5% of the total weight of catalyst and preferably 0.2 to 2% of this weight.

The support crumbly activity results from combining alumina to an acidic compound such as fluorine, silica, boric oxide, andc. By way of example, can be cited: the fluorided alumina, wherein the fluorine is 0.1 to 10%, preferably 1 to 5% of the total weight of the carrier, and silica-alumina, wherein the silica is from 50 to 99 % the total weight of carrier. Such carriers are well known to those skilled.

; The metal of the platinum family is introduced into the catalyst in any form, particularly in the form of a compound of metal such as, for example, palladium chloride or platinum-acid, which treatment is followed by an activation treatment and converting said compound to metal, by reducing or calcining, for example to a temperature in the range of 400 to 650 °c; then made the treatment by boron fluoride. The latter treatment will be ' preferably carried out in the presence of less than 20 parts of steam per million parts by weight of gas atmosphere.

The catalyst of the invention was superior to catalysts in which the boron and fluorine had been introduced by different means, including those in which the boric anhydride had been incorporated into the support.

The present method is more particularly applicable to gasoline and naphtha components in at least 90% of which boil normally between 30 and 220 °c and which comprise at least 65% of paraffinic hydrocarbons. These gasolines and naphthas should, preferably, have a low content of basic nitrogen compounds, it is to say a basic nitrogen content which is generally less than 100 births per million and preferably less than 10 parts per million.

This content clearcut easily be determined by assay to perchloric acid in acetic medium, using crystal violet as indicator.

The following comparative examples, exemplary non-limiting, illustrate the progress made by the method of the present invention:

Example 1. This example illustrates the use - of a known catalyst, platinum on fluorided alumina.

A platinum catalyst is prepared on fluorinated alumina by impregnation of beads (diameter: 1 to 3 mm) transition alumina (form eta) using aqueous hydrofluoric acid, followed by drying, calcination at about 450 °c, for one hour, impregnation of chloroplatinic acid in aqueous solution, drying and hydrogen reduction to about 450 °c.

The final catalyst contains 0.6 % platinum and 4 % fluorine.

Is passed over the catalyst, with hydrogen, a gasoline meeting the following characteristics:

73.6 Paraffins % 19.2 c/o Naphtënes vol. vol. aromatic 7.2% by volume sulfur 300 ppm by weight basic nitrogen 12 ppm by weight D. taxus 0,715

Octane number " of Clear

Research in " 61

Distilling SA t.m 74 to 140 °c

The temperature is 450 °c, the pressure of 70 kg/cm.² , the space velocity of 1 and the hydrogen flow rate of 1,200 liters/liter hydrocarbon treated.

Obtained, per kilogram load:

210 grams of propane;

150 g of butane;

100 grams of n-butane, and

520 g of gasoline having the following characteristics:

Paraffins napthenes 14.6 75.8% vol. % by volume aromatic 9.6% by volume sulfur and basic nitrogen.... less than 10 ppm D. receive 0,688 distilling t.m 30 to 140 °c SA octane number " of Clear

Research on " 74

The propellant may be recycled to the catalytic zone însqu ' virtually complete conversion. It can also be used as a fuel because of its low sulfur content and its good anti-knock, optionally after addition of anti-knock agent.

When a lowering of catalyst activity is manifested, it can be regenerated as follows:

In a first step, nitrogen passes during 15 minutes on the catalyst previously heated to 325 °c, at the rate of 100 liters/henre/liter of catalyst;

In a second step, the nitrogen is replaced by a mixture of 2% oxygen and 98% of nitrogen introduced at the same rate as before. The catalyst temperature gradually rises and then falls again;

In a third step, the temperature of the catalyst is increased to 475 °c and to pass the same mixture of oxygen and nitrogen than previously.

The catalyst temperature rises then up to 550 °c about and then falls.

The regenerated catalyst is analyzed: its fluorine content has fallen to 3.5%, which represents a loss of 12.5% of fluorine to the initial catalyst.

Example 2. This example illustrates - employing a catalyst according to the invention.

The catalyst is prepared as in example 1, but it is subjected to further processing according to: the catalyst balls is heated to the temperature of 300 °c, and passed, for one hour, on a liter of the catalyst, in a proportion of 60 liters/hour, an anhydrous mixture of boron fluoride and air, in the proportions of 20/80 by volume.

The load and the operating conditions are the same as in the example 1.

Obtained per kilogram load:

230 grams of propane;

170 g of butane;

110 grams of n-butane, and

470 g of gasoline having the following characteristics:

76.5% Paraffins napthenes vol. 13% by volume aromatic 9.5 % by volume sulfur and basic nitrogen less than 10 ppm D. " 0,685

Octane number " of Clear

Research on " 77

Distilling SA t.m 35 to 140 °c this oil can be recycled up to complete conversion.

When the catalyst is subjected to regeneration under the above condition to the example 1, it is found that there is not substantial loss of fluorine, result due to pretreatment, according to the invention, by boron fluoride.

Example 3. - The example 2 is repeated with a different charge, having the following characteristics:

75 Paraffins % naphthenes 16.5 vol. % vol. vol. 350 ppm sulfur aromatic 8.5% by weight basic nitrogen 22 ppm by weight D. 15 0,740 Distilling SA t.m 105 to 140° C.