DE1269756B - Process for the production of hydrocarbon fuels with a high calorific value - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

int. CL:

Clog

German class: 23 b - 1/04

Number: 1269 756

File number: P 12 69 756.2-44

Filing date: May 9, 1966

Opening day: June 6, 1968

The invention relates to a process for the production of hydrocarbon fuels with a high calorific value, which are suitable for use in jet engines.

In addition to a high calorific value, such hydrocarbon fuels must also have a high calorific value Have luminometer number, d. H. burn with a flame that does not glow if possible.

Since the tendency of a hydrocarbon fuel to have luminous, i.e. H. sooty flame burn, largely depends on its aromatic content, hydrocarbon fuels, which are to be used for jet engines contain very little aromatics.

Due to their boiling location, hydrocarbon fuels for jet engines belong to the gas oils, more precisely to the luminous oils.

Such mineral oil fractions are often obtained from higher-boiling mineral oil fractions by so-called hydrocracking manufactured. Due to the relatively high natural nitrogen content of the higher boiling However, mineral oil fractions quickly deactivate the catalysts. This can be done by one from the French No. 1,318,389 known special procedure can be avoided in which the catalyst is first covered with ammonia, thereby causing a deposition of the nitrogen compounds in the 10 to 1000 TPM nitrogen-containing feed and thus increase its service life.

Nevertheless, the hydrocracking process according to this French patent cannot satisfy if the luminous oil fractions produced by this process are used as fuel for jet engines should be, among other things because the process products due to the relatively high aromatics content of the feedstock also contain significant amounts of aromatics.

From the journal "Chemical Engineering Science", No. 2 (1953), pp. 69 to 73, it is known that petroleum waxes catalytic hydrocracking are accessible and that also as fuels for jet engines suitable luminous oil fractions can be obtained.

However, this known hydrocracking process has the disadvantage that under conditions at which a high percentage of the feed is converted in one pass, one too far ongoing cleavage, which leads mainly to petrol and products with a lower boiling point, takes place, while under conditions under which the desired luminous oil hydrocarbons in a satisfactory yield, based on converted starting material, process for the production of Hydrocarbon fuels with a high calorific value

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr. E. Jung and Dr. V. Vossius, Patent Attorneys, 8000 Munich 23, Siegesstr. 26th

Named as inventor:

Emil Oscar Kindschy, Pasadena, Tex. (V. St. A.)

Claimed priority:

V. St. ν. America May 10, 1965 (454 747) - ·

arise, the conversion per pass is too low.

It has now been found that petroleum waxes which contain less than 10 ppm nitrogen, by catalytic Hydrocracking with high conversion per pass in hydrocarbons boiling below 288 ° C can be converted, with a high yield of hydrocarbon fuels suitable for jet engines is obtained by adding 20 to 100 ppm to the petroleum wax serving as the feed basic nitrogen added.

The invention thus relates to a process for the production of hydrocarbon fuels high calorific value with at least 30 weight percent of a petroleum wax per pass in the presence a catalyst consisting of a hydrogenation-dehydrogenation component on a solid, acidic active, refractory oxide carrier consists of hydrocracking in hydrocarbons boiling below 288 ° C be converted, which is characterized in that a wax charge, the contains less than 10 parts by weight of basic nitrogen per million parts by weight, 20 to 100 parts by weight of basic nitrogen, based on 1,000,000 parts by weight of the feed, are added so that the Hydrocracking at a temperature between 288 and 399 ° C, a pressure between 35 and 140 atü, a space velocity of 0.25 to 5 parts by volume wax / hour / part by volume catalyst and a

809 558/328

3 4

Molar ratio of hydrogen to charge of special fluorine, suitably in an amount of

5 to 50 is carried out and that the hydrocracking at least 2 percent by weight, based on the ge

product is fractionated, from which a whole catalyst is reinforced,

be ren boiling between about 149 and 316 ⁰ C fraction as feed for the inventive Verfaheinem calorific value of at least 10500 kcal / kg 5 off preferably petroleum waxes used, the

is separated, and that optionally from the hydro in the refining of waxy lubricating oil bases

cracking product incur an above 288 ⁰ C boiling paraffin. Distillate or residue waxes can be used

fraction separated and used for hydrocracking in the circuit. As "distillate waxes" are

run is returned. Waxes used in the refining of The reaction conditions in the hydrocracking stage apply to distillate lubricating oils, while the

In the process according to the invention, the relative pressure “residue waxes” refers to waxes that

moderately mild. The following working conditions apply during the refining of residual lubricating oils,

preferred: like »bright stocks«, are removed. Distillate lubrication

Temperature 288-399 ° C ^e f _A ^and ^ ™. ⁿ _{A have} ^them derived waxes

η I YQ ι- 126 atü ¹⁵ boiling points at atmospheric pressure of at least

Space velocity ;. ' Ibis 3 parts by volume 288 ° C and generally contain no more than

Waclis / h / ^ea percent by weight of hydrocarbons that

Part by volume boil ^about 316 ° C. Residual lubricating oils boil

Catalyst, of course, even higher.

Molar ratio H to 20 The distillate waxes are generally paraffinic

Charge ² ^ q ^ ₅ 25 ^scner nature, the ratio of η-paraffins to

Isoparaffins reversed their molecular weight

Since the petroleum wax is almost always only very proportional. On the other hand, the residue rings Have sulfur and nitrogen content, can wax microcrystalline wax or high-melting wax for hydrocracking contain both a sulfur 25 paraffins or both. Actually all are more resistant and sensitive to sulfur residue waxes from a mixture of microlicher Catalyst can be used. The hydrogenation crystalline and macrocrystalline growing together-dehydrogenation component of the catalyst is set, but they can preferably be separated into separate wax fractions are split up from one or more of the different ones, which are essentially microns Group VI and / or Group VIII metals 30 are crystalline or macrocrystalline, of the Periodic Table of the Elements and / or As wax charges for the inventive the oxides and / or sulfides of these metals. Special methods are either raw or purified The oxides and sulfides of molyb waxes are more suitable. Depending on their degree of purity, they contain Danish, tungsten and chromium and the metals iron, most waxes at least some oil of about that Nickel, cobalt and platinum and their oxides and have the same molecular weight as the wax. It's solid sulfide. If desired, the hydrogenation can be set, that also waxes with a much higher Dehydration component more than one of the oil content, d. H. up to about 30 weight percent, as named metals, metal oxides and / or metal sulphides contained in the feed for the process according to the invention, particularly good results with Kata- are suitable. From an economic point of view analyzers have been obtained, the compositions are seen as the oleaginous waxes as feeds genes of two or more oxides of molybdenum are preferred. A particularly suitable feed for Contains cobalt, chromium, tungsten and nickel. The method according to the invention is the so-called Amount of the hydrogenation-dehydrogenation component "soft wax" that is a by-product of de-oiling is preferably between about 0.1 to 50%> based on raw wax with a solvent, based on the weight of the entire catalyst. 45 the raw wax being obtained by dewaxing distillate ais Catalyst supports are preferably silicon and residual lubricating oils with a high viscosity and / or aluminum oxide is used. However, health index has been obtained.

Other refractory oxides can also be used, such as Mont- In the well-known hydrocracking process is a morillonite, silicon dioxide — magnesium oxide and the relatively high nitrogen content of the hydrocarbon zeolites and molecular sieves are used. In 50 loading undesirable and must be kept to a minimum In some cases it is desirable to reduce the activity of the in order to achieve rapid deactivation Catalyst by adding acidic substances, it is advisable to avoid the catalyst. Now, however, is over fluorine and chlorine, to amplify the amount surprisingly found that those present Elements preferably at least 2 weight units of nitrogen in the feed so far percent, based on the total catalyst, is advantageous than that used according to the invention. th, comparatively mild conditions of the hydro-If a catalysis resistant to sulfur the selectivity with regard to the production is used, the catalyst support consists of hydrocarbons, which are preferred within the luminous oil of silicon dioxide and aluminum oxide. boiling range is increased considerably, Preference is given to a support which is about 50 to 90% and 60% without significantly reducing the catalyst life 70 to 90% silicon dioxide and the remainder is reduced.

Contains aluminum oxide. Among the suitable nitrogen compounds that the

However, hydrocracking will be included in the inventive feeds

according to the method in the presence of an ammonia, organic amines, z. B. triethylamine,

Sulfur sensitive catalyst, e.g. B. one of 65 heterocyclic nitrogen compounds, e.g. B. pyridine,

Platinum catalyst, then there is the cata- and other cyclic compounds with nitrogen

Lysator support preferably made of aluminum oxide, its substituents. For economic reasons, each

Acidity due to the incorporation of chlorine or especially ammonia is preferred.

The yield of hydrocarbon fuel with a high calorific value can be increased significantly if the ^{paraffinic residue remaining after the fraction boiling between 149 and 316 °} C. has been separated off is recycled. Therefore, the obtained in the separation of the boiling 149-316 ⁰ C fraction from the hydrocracking product above 316 ° C boiling fraction is preferably recycled in the circuit for hydrocracking.

The hydrocarbon mixtures which boil from 177 to 288 ° C, are suitable as jet fuel as the hydrocarbon mixtures with a further boiling, a boiling 177-288 ° C fraction from the hydrocracking product is separated preferably and the above 288 ⁰ C boiling paraffinic residue appropriate for hydrocracking returned.

The end product of the inventive method, ie the points 149-316 ° C, preferably 177-288 ⁰ C, boiling fraction in addition to the high calorific value and a high Luminometerzahl.

The Luminometer Number (LN) of a fuel is the empirically measured luminosity of one by burning of the fuel in a special, previously described flame generated. (The details of the luminometer test are in "Tentative Procedure for Operation of Luminometer" from March 10, 1959 by Erdco Engineering Corporation). The luminosity corresponds to the theoretical one chemical energy that is converted into light instead of heat when the fuel is burned will. A high luminometer number (low luminosity) is important for several reasons:

1. The chemical energy converted into light does not contribute to the expansion of the combustion gases. So is the theoretically available chemical energy with a glowing combustion only partially converted into pressure energy for the aircraft.

2. The luminosity is generally based on glowing carbon particles that have to be _{burned to form CO 2} in order to achieve the maximum available thermal energy of the fuel. The fact that part of the fuel is incompletely burned means that neither the potentially available heat nor the possible volume of gas is reached.

3. Small, solid particles in a high velocity gas stream can cause erosion the turbine blades.

When using hydrocarbon fuels produced according to the invention as jet engine fuels, the above problems practically do not occur, since this product has a luminometer number of has about 100.

The example illustrates the invention.

contains only the normal 2 to 3 parts by weight of nitrogen. The following results are obtained:

Influence of addition

from basic nitrogen to wax charges (50% conversion per pass)

example

working conditions

Pressure, atü

Space velocity, parts by volume wax / hour / parts by volume
catalyst

United feed ratio

Molar ratio of H ₂ to wax ..

Temperature, ⁰ C

H ₂ consumption, Nm ³ / m ³ fresh
feed

Yield of luminous oil (boiling range from 177 to 288 ° C),
Weight percent

Luminous oil properties
Specific weight, kg / m ³ ..

Calorific value, kcal / kg

Freezing point, ⁰ C

Paraffin, volume percent

Naphthenes, percent by volume ...
Aromatics, volume percentage ...

Feed nitrogen content

(TPM) 2 to 3 50

105

1.0

2.0 14.4 362

115

45.9

105

2.0 14.3 388

766 767 10518 10513 -52 -53 91.8 90.2 8.1 9.0 0.1 0.8

60

A wax containing 20 percent by weight oil is _{decomposingly hydrogenated over a W-Ni — SiO 2} —Al ₂ O ₃ catalyst at about 50% conversion per pass. Two runs are run, 6g, one time adding tri-n-butylamine to the feed to a total nitrogen content of 50 parts by weight and the other time adding the feed. The results show that the addition of basic nitrogen to wax feeds containing less than about 10 ppm nitrogen contain, the selectivity of the process in terms of the yield of luminescent oil with a high calorific value increases quite significantly. For this reason, 20 to 100 ppm of basic nitrogen are added to the low nitrogen wax feeds to be reacted.

Claims (5)

Patent claims: 1. A process for the production of hydrocarbon fuels with high calorific value, wherein at least 30 percent by weight of a petroleum wax per pass in the presence of a catalyst consisting of a hydrogenation-dehydrogenation component on a solid, acidic, refractory oxide carrier, by hydrocracking in below 288 ⁰ C boiling hydrocarbons are converted, characterized in that a wax feed containing less than 10 parts by weight of basic nitrogen per million parts by weight, 20 to 100 parts by weight of basic nitrogen, based on 1,000,000 parts by weight of the feed, are added, that the hydrocracking at a temperature between 288 and 399 ⁰ C, a pressure between 35 and 140 atm, a space velocity of 0.25 to 5 parts by volume wax / hour / part by volume catalyst and a molar ratio of hydrogen to charge of 5 to 50 and that the hydrocracked product is fractionated , from this egg ne between about 149 and 316 ⁰ C boiling fraction with a heating value of at least 10500 kcal / kg is separated, and that optionally from the hydrocracked product separated a paraffin fraction boiling above 288 ° C. and used for hydrocracking in the Cycle is returned. 2. The method according to claim 1, characterized in that a catalyst is used, whose Hydrogenation-dehydrogenation component composed of one or more Group VI metals and / or Group VIII of the Periodic Table of the Elements and / or one or more oxides and / or sulfides of these metals. 3. The method according to claim 1 and 2, characterized in that a catalyst with 0.1 to 50 percent by weight hydrogenation-dehydrogenation Component and a carrier made of silicon dioxide and / or aluminum oxide is used. 4. The method according to claim 1 to 3, characterized in that that a catalyst whose support is about 50 to 90 percent by weight silica and contains about 50 to 10 weight percent aluminum oxide is used. 5. The method according to claim 1 to 4, characterized in that that a catalyst containing fluorine and / or chlorine is used. Considered publications:
French Patent No. 1,318,389;
Chemical Engineering Science, No. 2, pp. 69-73 (April 1953). 809 558/328 5.68 © Bundesdruckerei Berlin