DE1593042A1 - Catalyst and catalytic process - Google Patents

Description

Catalyst and catalytic process

The invention relates to Katalya processes, at where a new type of catalyst is used, and on Process for the production and use of such a catalyst

Ee is “one of the aims of the invention, a new catalyst to create »dtr is economical, and timely for dtn its resistance to catalyst poisons, «ine he · mechanical strength and long service life is typical, A further aim of the invention is to provide a catalyst create »for various catalytic conversions including Dehydration reactions »progressing under dehydration Cyolization reactions »Heform reactions» Hydrocracking reactions, Isomerization reactions, Ilydration reactions and so on. Ks is also a target Invention to create a catalyst that has the properties free radical · has »whereby dls implementation of the mentioned catalytic conversions is promoted

£ ln further object 1st to üchüffen a catalyst which is easy herstellbur from inexpensive starting materials, and asohanlsohe for the "in" wag · strength

009830/1879

BATH

both when used in a fixed catalyst bed as also typical for catalytic) processes in the liquid phase is, and also a long service life and • resistance to the usual catalyst poisons is typical.

For those used in commercial processes for dehydration, aromatization, etc. used conventional catalysts generally have metals and vetal oxides and other metal compounds found as the active, catalytically active components application · such catalysts are in general quite expensive, especially when using a precious metal catalyst, Like platinum or palladium, for example, such catalysts are also effective in their effectiveness Adversely affects water vapor, which permanently deactivates conventional metal catalysts

Ee has now been found to be a highly effective catalyst for coal aerosol conversion reactions such as dehydration, dehydration cyclization, reforming, isomerization, dee hydrocracking and hydrogenation, consists of a carbonaceous substance that occurs in the condensation of unsaturated hydrocarbons incurred, and "was preferably of some form of carbonaceous substance, tile paramagnetic. The preferred Types of carrier material are in the below Table listed * This table also lists some dsr activators which, although not essential, do often in an advantageous manner to improve the beliefs of the invented catalyst can be used.

Trftgermaterislltn Dehydration and gelation proceeding under dehydration

TrUgeri Ganma aluminum oxide, Kte ~ aluminum oxide, alpha aluminum oxide, Magnesia, Sllioa, Silionte, Titrtndloxyd, Caloiuaoxyd, Zlrkondioxyd, whereby

009830/1879

BATH

the acldity factor (as defined below) is not more than 2.0

AIctiva'.oren: alkalis (e.g. Na, K) t alkaline earths (for example · Cs, Mg); the group IB (for example Cu, Ag); the 'group HB (for example Hg); the group VIB (e.g. Cr, Mo, W); group VIII (e.g. Fe, Co, Ni, Pt, Pd).

Reforms. Hydrocracking Clones. Isomerization

All irHger for the carbon-containing interial will be the Tri ^ er materials listed in the above group in a mixture with at least one of the following aoidisehen Components used!

Silica-aluminum oxide, silica, silica-magnesia, Gamma or Kta aluminum oxide, with the Aeiditätaiaktor (as demarcated below) is not below 3.0, either without, as a precautionary measure However with halide (over 0.1 wt. ^ Cl or F).

Activators Cl ₉ F;

■ Group VIII transition metals, such as Pt, F ·, Coj group VIB (Cr, Mo, W).

Hydrogenation

Trügen ^ f-AIgO, with an acidity factor dee Alumlnluuojcyde, which is not more than 2.0

Activators are the metals of group VIII, belapielswei Pt, Pd, Ru, Rh, fie, Ir, in a proportion τοη 1 to 2.0 Clew.J * of the entire katalveatoraeng ··

009830/1879 __

BATH ORIGINAL

In the case of τοη carrier ferrules, which are to be used together with the carbon-containing substance for dehydrogenation reactions and dehydrogenation proceeding cyoiialerungereactlonen, it is often mentioned that ·· a τaaamengeate catalyst τaοη lower alloys can actually be used Carrier material is anyway achon τοη from the outset by aolehe auacelohnet, duroh da «Blnaunehaen τοη compounds of the alkali metals or the alkaline earth metals In a proportion bareloh τοη 0.1 bla 5 ^e ew.jf aoloher compounds, calculated ala metal and beaogaegewa on daa Gehaltigeneaateaatea Catalyst to be obtained. Some alkali metals have the property of catalytically triggering the watergae reactions, which also occur when Waaaerdaapf is used as an extender. The method of measuring the aoidity factor is discussed further below.

Other metal activators can cause erosion an eynergetic lately effect on the carbonaceous Phaae must be taken care of. Dieeae Metallaktivstorea can in veraohiedener whale · · have a beneficial effect. You can get dehydrated of various organ pools Beschiokungeaateriali a lu promote unsaturated intermediate products, which then continue condensate and the more active carbonaceous Phaee form. In this sense iat ·· their function, sur formation of the desired, finished Katalyaatormaaae. aside from that Metals can also retain the activity of the formed koalenateff Phaae, the dleae activity greatest parta, if auea not exclusively au thanks iat, veretärkea.

Although the invention painted dlapergierte Kohleaetoffkatalyeator-Grundubetana nloht In the first line a hydrogenation catalyst lat, ao throws theeae Grundaubatanf dooh, fall » man al · auaaamea with a metal such as belaplelewelee Platia or palladium is used, considerable hat «en ala hydraulic catalyzer away·

009830/1879

In the case of a catalyst, which is used for forming processes, ■ Suitable for isomerization and turn hydrocrackers. A noticeable acldity is desired. The halide actuators can also be used to increase the acidity · Also the metal oxides of group VIB, for example the oxides of Chromium, molybdenum and tungsten can be used as activators find, »calibrate the AcidItHteg & increase and at the same time the cehydration actlvltät »u are suitable.

It has now been found that a highly effective catalytic converter duroh for the catalytic reactions described above the use of deposited carbon is obtained in the condensation of an unsaturated, carbonaceous Feed material in the form of a non-volatile, carbonaceous one Substance of higher molecular weight containing hydrogen in a low atomic ratio to carbon, accrues · The Beschiokungemeterlalien are preferential Hydrocarbons of unsaturated character, for example oils Bensol and other aromatic hydrocarbons, for example Toluene, xylene, ethylbene, styrene, co-ethylstyrene and Naphthalene) aliphatic saturated and unsaturated hydrocarbon elnechlleOlioh methane, Athens, propane, butane and Compounds with a longer chain, such as, for example, Cyolohexane, Deoan, Dodtcan and the like., As well as the corresponding »olefinisohen uad a three-bond containing compounds, such as for example ethylene, propylene, butylene, dl amylene, deodorant, Ifcdeoem, Cyolohtxenj Diolefin ·, wi · btispitlswelse Butadiene · Cyolopentadiea, Isopren uad Aoetyl «m and the like. Carbon is preferably derived from an unsaturated grain inert material which is released during the period of separation becomes · Dooh can the unsaturated hydrocarbon auoh formed in the HeaktionsgtfMQ «« rd «n, for example · daduroh, lasa one a saturated Besohiokun "" material, see B. lutaa, see below a carrier germattrial such as aluminum oxide, mn the sloh then ine dehydration of the saturated saturation material

15930Λ2

See, and Eutadienes fully, A soloherna'Sen deposited carbon can be dispersed on the carrier material, in that the abovementioned Besohiokungeaaterlai in the hotest Heaktlona.jef? i3 introduces, for example at a temperature of 200 to 1400 ⁰ C, whereby a preferred temperature range is the tone 300 ⁰ C bit 900 ⁰ C and a particularly preferred range is that of 400 ⁰ C to 800 ⁰ C. Flow velocity and pressure are not critical, so that one can work at atmospheric pressure. The carbon catalyst can also be deposited on the walls of a tubular or other form of catalytic peak vessel. Silica-l'onerdegele, aged or deactivated) silica-aluminum oxide Kraekkatalysator, magnesia, diatomaceous earth, bauxite, titanium dioxide, natural as well as acid-treated clays, for example the Super-Filtrols (Super-Piltrols), Attapulgus clay (Attapuljus clay), , Magneslumsllicat, Carborundtui, zeolites as well as »sollthisonea molecular sieves (seolitio aoleoular selves) and 3wlsohenr $ uaen forming elements such as rooms and balls made of keraalka material, brick chippings, ZiogelteileB and the like." dta are introduced into the Beaktlontgefaa, exist or contain these materials. The carrier material can contain an activator oil, for example satrlua or platinum, which would have been subjected to a lapregnation or test process before the carbon was deposited. Dooh, these active blinds can be brewed on the carbon "toff" bsohei1ungen ^ ath ^ ltenie Mlaohungs "s ···, since ··· asn belcplelswelse elaea activator old of the delivery ester, or also by direct application of the · activator · duroh Besyrühea or Duroatrtokea the catalyseraisohimg la tea lteaktloosgeffti e4 «r an in a« sndsren defl · prepared Mlsehmag old egg * ter- • stage of the activator ·, for example old latrluanitrst, if · astrium should be applied ·

009830/1879

Generally speaking, the invention is based on the finding on the fact that carbon deposits, which are obtained when unsaturated hydrocarbons condense, act as a catalyst for the here unsetsungen discussed τοη hydrocarbons extraordinarily are effective. In any case, the special font of carbon obtained in this way is by no means a pitch or coking product exhibiting harmful properties, since the catalytic one Diminishes activity, but is rather self-explanatory catalytically active insofar as there are dehydration reactions, cyelislerungsreaktloaem "Md such. Promotes"

When using the catalyst according to the invention sun dehydrate, au what purpose the carbon on one Carrier τοη low aoidity, for example about (taausa-Alu- ■ iniuaoxyd, since an avidity factor τοη does not exceed 2, ο, is deposited, it is found that sioh the carbon Deposition at an initial speed that is less than ten times that of nan over a Silioa-Aluniniunozyd-Kraok catalyst is obtained. Auohweis the carbon deposited on a carrier τοη lower aoidity «A higher dehydration intrinsic activity than that a carrier τοη high Aeiditat deposited, such as him used in hydrocraxes · The · is due to the fact that 4 carbon is in a more strongly dispersed form, in which it is easier to interact with the carrier material, which increases the catalytic activity weather".

We can also see that the invention catalytically active carbon in the course of the described here Dehydration, cyanolation and other reactions no strong Abaoheidungen τοη coking stains forms. In fact, you can also modify the sun settings τοη hydrocarbons at relatively high

009830/1879

BAD ORJGiNAL

Temperatures can be carried out at which there are considerable carbon dioxide separations kosuaen Urde, while χ together with dom Kor ^ else at a 3e. It is from 0.1 to 30 percent by weight or preferably from 3 to 20 % carbon on an Γη er such as in the case of aluminum inluKOXyd, where aioh refers to the addition of atalyeatic acid. -ε was found, aes k aktlaen iieaer 4rt l. "long, uninterrupted process-f yirten, / although there is no need to regenerate the Kutal ^ aator. liui'ig"

i; he oilers the .leaktionemeohanle- ■ s, the erfindun duroh eng causes ^ H emiiseen Koiilenstoffkatalyeator / ground eaKtionaaeohanisous, and zir J / UiChiUhrung discussed herein, various Umeatzuri he ^: oeitrafen are fully understood nloht £ .8 was j '.-dooh found that a clear kutalytleoJae effect is achieved, without the need to blow, for the koi.ventioniilkn, -iua stalls or to operate metal compounds existing catalysts.

A tehr ^ irksaSDes analytisohes aid funds, de "geniuses to study the vorli ^ katalytiechen Ersoheinungen CN" ending found hit, iut .lie I-lektronenepinreaonanxanalvee, la naohfoloetiden short: -% 1ε · · ί referred ί. So beiftplel * - T * eiee became an auc ei μ es. ; Ui an icjtälytiooh inactive "O" aea-ÄluainluBoxyd applied carbon atoli (originally produced from the thersl60h "n ^ crcetzun ^ of styrene ·} bedding Äatalyeutor subjected to an a ·» analysis, then «he for dl · leaching to -thylbene has been used «rar» The io-i analysis er ^ iot a uei 9.5 GHz ^ eaees «» · »intensive line« At room temperature the Jiuea value (g valu «) is 2.0027 and the line Hulbwertöreite is 500 iiilligau ·« "The absorption is intense, before it can be seen that there is a significant number of unpaired electrons in the active carbon catalyst."

009830/1879

The presence of unpaired electrons is essential Quantities seem to indicate that you are capable of these electrons are, under the reaction conditions, as they are during overhydration, with acid cracking, with heating, with flavoring and so on prevail, '■'; fiber atoms from hydrocarbons split off and thus trigger reactions in which free adicals appear.

In the case of dehydrogenation, this conversion takes place in accordance with the reaction mechanism involving the carbon catalyst the form of a splitting off of; 'uaseratoff atoms from the BeöChiokun-emoteriala hydrocarbon. The ones on the carbon any unpaired electrons present are due to the recombination the vaaseratoffatoae to molecular /,., hydrogen and regenerated by the addition of rta8t> er ,, toffatomen to free radicals. The oxygen atoms formed by the splitting off Free radicals can then be subject to beta splitting, cracking products are formed or the reaction proceeds, as in the dehydrogenation of 2,4 »4-trimethylpentene-2 was found to cause a 1,2-vinyl rearrangement to occur of a 2,5-dimethylhexene-2-radical as an intermediate for the final cleaning of p-xylene continue

The aromatization of acyclic hydrocarbons takes place in a similar way by dehydration to trienes. the Trlene are cyolized on thermal ■ ege from cyolic Cg dienes, which are then dehydrated to the aromatic product. An example of this latter pail is flavoring of n-heptane with formation of toluene.

The essential component of the catalyst according to the invention, whether this is applied to a carrier material or not, it is a carbon-containing phase. This carbonaceous Phase shows, apart from the carrier phase,

BAD ORJGJNAL

009830/1879

Generally, a carbon content of 50 üew. # and above, and preferably from 60 to 99 wt. ^ ₁ wherein the remaining border for the most part consists of aaserjtoff and Ueteroatomen and only small or trace amounts of metals are present. The higher carbon content occurs when there is a low content of elements other than hydrogen and carbon. For the carbon-containing phase tine highly unsaturated constitution is typical, such as in a low 'asBerstoff / carbon Atomverhaltnie (hereinafter referred to as the H / C-Verhftltnis) of the carbonaceous su l-Huae recognize _b' is ibt. The H / C ratio here, as has been found, is not more than 1.5 or preferably not greater than 1.1 and very particularly preferably it is in the range from 1.0 to 0.1.

Analysis of the carbonaceous phase obtained from a hydrocarbon feedstock reveals that it consists mainly of carbon and fuel. However, an active mixture can also be produced when heteroatoms are present, such as oxygen, sulfur, nitrogen or halides. Here, for example, the formation of a carbon-containing catalytic converter on a porous carrier material of alpha-aluminum oxide can be cited, if this is used as a substrate on which a condensation of quinone, CgR, in the catalytic heating vessel without additional introduction of oxygen or water components \ 0 ₂ "to a carbon-containing phase" This creates a carbon-containing catalyst which, as his analysis shows, contains measurable amounts of oxygen. Similarly, a catalyst containing substantial amounts of nitrogen can be obtained from quinoline, ^ gHyN, while the carbonation of xhiophene, CH.S, produces a sulfur-containing catalyst. In any case, however, the H / C atomic ratio is not greater than 1.5 and usually not greater than 1.1.

009830/1879

In addition to the forms of dispersed carbon, which can be obtained in the above-described manner by condensation of unsaturated organic molecules at high temperatures, other sources are also available which also provide the desired dispersed carbon. In addition to the udgangskoaponenten / udgangskoaponenten containing unsaturated molecules, which are generally introduced in the form of niohtpolyeeriaierter Yolyeeriaierter YoIeküle in the gaseous state, a further source includes the polymer / ompononten, which are then subjected to a pyrolysis "with higher unsaturated types of molecules so that the dispersed carbon can be obtained. This pyrolysis step can be carried out in a vacuum, in an inert atmosphere, such as nitrogen, or, if desired, in an atmosphere containing oxygen-containing molecules, such as oxygen, mostly outside, crude dioxide and carbon monoxide For example, for the deposition of hollow materials, one can proceed in such a way that an organic polymer such as polystyrene, which should have a molecular weight of 5,000 to 500,000 meters by meter, is dissolved in a suitable solvent such as benzene or dioxane * contains a suitable coating from 1 to 50 weight percent of the polymer. The LJsung of olyacren * v ^ irü then coated on a porJaes Träe'eraaterial of low cidit'it, beispiilsweise on Aluainiuaoxyd, magnesia, or diatomaceous earth and the solvent by £ rwfirmen or applying a vacuum removed, d <: ss the polymer on the Carrier material is evenly distributed. The mixture is then dried and subjected to -tyrolyse, for example in the Fora that the aan "iechung to a temperature of 2QO ⁰ C to 800 ⁰ C heated so the k'.talytisch active carbonaceous Fh .se produce su.

When using organic polymers to generate a dispersed carbon phase can be made from the organic polymer Kohlwaaseretoffürten »ie for example polystyrene, Polyaetfaylstyrolen, iolyuthylen, polypropylen, as well as also from

003830/1879 bathroom

Polymers containing heteroatoms, eo for example iolyaorylnitril, i'olyissethacrylonitrile, polymethacrylic acid methyl ester and other heteroatoms, for example sulfur or halogens, zui Example Cnlor, containing polymers. For example Foly vinyl chloride can be used or ee Fluorine also contains small amounts of transition metal ions present B ^ in. Serve toffe k inside ii. Form of ./onomers, copolymers, iiomopolyiaeren, ternolymers and the like. In use come·

Auoaer the Betoniere above aul _t e led carrier materials uitid iuoh the various conditions described in the previous preceded poröeen x'rig-er, inebeaonaere the inert oxides and mixed oxides dee Aluninlume, oilioiums, ^ a ^ nejiu »», Zirkoniuee, Xitane, etc. · Wakes up. Therein the β Aillkirlioh formed · StUoke, Kigelohen, it> »xtruded or cast Forca and the like. la ICO Angatra, the value of 0.3 l / g of the carrier material does not exceed and, preferably, the value of 0.2 µl / g of the carrier material should not be exceeded. In advance, these bearers should also have a low aoidity typleoher catfish, which we shall now have to deal with. In comparison to the sources according to the invention for condensed carbon compounds, there is an activated carbon, which comes from a bituminous coal and which has an inner surface of 1000 square meters per gram and a volume of pores with a size of 100 angstroms from et al / .3 al / g has a very poor selectivity, η i ".lieh a 38-percent selectivity with an 8 yigen conversion in the dehydrogenation of ethylbenzene to styrene This is attributed to the impairment of the selectivity by the small pores, you the same reaction under the same reaction conditions If it is carried out with a catalyst which contains 1? .5 Ge *. ^ carbon on Gaama aluminum oxide, a 96% electivity with a 43% change

009830/1879

Conversion results in · Dae conversion ratio let defined here ale the numerical expression for that portion of the feed material, which has been converted to styrene and the selectivity ratio is defined as the ratio of that Proportion, which was uragewa delt in styrene, to the total amount of the converted shares

The carbon-like catalyst according to the invention can be subdivided in two ways from those according to the prior art, be I ep ie 1 owe i se of those that are used in cracking catalysts or in thermal cracking processes, as well as activated carbon. The catalysts according to the invention contain carbon in a more strongly dispersed form and also consist of mixtures in which the carbon dispersed on suitable Irfigermaterialien is subject to interactions between the carrier and the carbon, which increase the catalytic properties. It can be established that the specific surface area of a catalytically active phase is greater and the catalytic activity is greater, the finer the distribution of the relevant phase. The carbon residues formed by thermal cracking or obtained by deposits on cracking catalysts are not so finely distributed, ie the degree of diapersion of a carbon deposited on the carrier materials according to the invention with low aoidity can be determined by measuring the sheet metal spin resonance (KSR). If oxygen is absorbed by carbon at chewing temperature, which is, among other things, a reversible process, the spin movements of the unpaired electrons on the surface of the carbon are dermally expanded so that they can no longer be detected. In the presence of oxygen or air, only splash movements in the interior of the carbon mass can accordingly be determined. In a vacuum, on the other hand, both the surface and internal upward movements are determined as a total value.

BAD OFFICIAL

009830/1879

~ It can thus be determined by measuring the apine concentrations in air and in vacuum (each with the same or can be made with different samples) the Relationship of the urntapin movements to the inner opinion-consciousness conditions can be determined. The more finely distributed the carbon, the higher the ratio R of the spin motions in a vacuum to the opinion movements in air.

: a was found (Table I) that the deposited carbon on acidic Ir ^; i ^ er materials are not so finely distributed! like on -wheels ait lower; vcidit ^; it. Indeed, it has been found that an R-Vert greater than 5 is preferred for higher catalytic activity. β Iie3 calibrated to demonstrate that a finer distribution from other JrUnden than that of a b.oßen enlargement of the inner surface is advantageously of Kohlenolo.fis · 3o is beis _z .leihweise in Table I held, spin movements IASS the total number of surfaces · the iJilica -Aluminum oxides (g ~ catalyst) is at least comparable to that of aluminum oxide of lower acidity, although the k · ..tal. table activity is lower. Ks is assumed that whoever is finely dispersed carbon with the carrier in an intimate ^ he ^r lhrung and '' lektronon-xechselwirkungen with the ^Ir: i. <Jer received that increase the catalytic activity, bo affects the finer distribution twice from namely, in an enlarged surface and in advantageous interactions with the carrier material. Similarly, the higher activity of aluminum oxide A, which contains sodium, cannot be traced back to a higher total value of the pin movements or to a larger number of surface pin movements ; it is possible that the sodium on the surface of the aluminum oxide acts as an electron activator which increases the catalytic activity.

009830/1879

Table I *

Carrier or type of catalyst

& G (number of * .pinbe- ^{i #} j number of cU3pin-

· Relative ka-

be * ejgun _t , en in air ^ in vacuum tal.v tables

'10 .ig ^ Kofclen- ^ Pinb; » _egg .
^{in air}

18th

2 / Well on Alutniniu »· oxide A

O (O OO U) O

Aluminum oxide of lower acidity

, 2

93

0.0035

Aluminum oxide A.

11.5 8.9

77

0.0059 υ, 130

** evacuation 12-16. 'landen, 400'J, 1j ^ wellen-Leistun.jspe.jel Vor ^ enon ^ e- .. "u catalytic A5ctivit: t "entairecr.en ßujiten-1 in butn-iien at 54> j U53

590

10.1

4.91

Aluminum "1ü
oxide B; , 0 7.0 39 0 , 042 : ο , 235 166 5.38 Silica-alumic acid * 29
nium oxide A i cracking
i katal., - JÄ-oi , 6 23 80 9 , 36 31
I.
I.
1 .6 2.5 2.05
I. Silica-aluml-!
nium oxide B, "J27 ,8th 26th 92 1. .27 37 2.53 2.09 Filtrolton 8θΌ "I 1 .04 ο, 3u 29 0 , 2o1 25th , 10 1.15 i under 1 0.5 * it on i 3aurer 22
Zeolite type ϊί hydrocracking
! catalyst , 7 28 123 13th , 99 61 , 63 1.99 about 2

ΐϊ ... * All: «β ;; sunken are with the ^ slight micro-
^ jn ^ aef fek: te are absent .. .n lei 3 column "relative
.- .. ir.heitei .eini completely: nii.jen .im * · ndlun ^ of

It is clear that carbon, activated carbon, coking pieces & d « and carbonaceous mixtures of various types in many different ways and very different ages>. Some ntj chefs can be made, with a lot of these Substances are paramagnetic in varying »extent · Ks however, found that the catalysts according to the invention are very strongly paramagnetic and very finely dispersed, the following properties exceeding the general range of the old de EdR spectrometer can detect measurements made

A. The g - »th (spectral analytical splitting factor) are in the range from 2.0 to 2.1, but preferably in the range from 2.00 to 2.01

B. The spin concentrations are in the range of

1 χ 10 "* eis 1 χ lü ° * ⁵ spin motions per carbon atom.

C. The line widths can be up to 100 outside, however, preferably exceed a width of 10 SauQ not.

P. Sas relationship of the spin concentration la Yakuua to the The concentration of opin in air is greater than 5 # where ice preferred range that is from 10 to 5000

The following example shows the Jbestlaaung the aagnetlachen i.lgenechal'ten of the catalyst described below, the Ausführungebeispiels 3. Tmr spent catalyst, the NaOH completion of the test drive was removed from dea Reaktionsgefäl, "ird both before the evacuation NaOH at 10 ~ ⁵ aa Hg investigated in an electron response / resonance spectrometer. The oil nal is very intense, which shows a high spin concentration. The ratio of the spin concentration in vacuum to that in air is 590. The spectrum is measured at 9.5 SHs using a Varian V4502

009830/1879 ₀ ^

X-band spectrometer with a calibrated analysis frequency range According to Varian-Field (Varlan Pieldial calibrated sweep) was equipped and had a 6-inch (15.24 om) magnet, measured. The sample is measured in a -iuarzrohre. The g-Aert is determined by comparison with crystalline diphenylpicrylhydrazyl

During the test drives for dehydration described above from ethylbenzene to styrene

(1) activated carbon and

(2) Carbon, Oer to 12.5 ow. # On an Oamma- ^ lumi- · nium oxide of low acidity (factor 0.1) applied was

were the asene concentrations of pink in a vacuum (Spinbowe- Lung / carbon atom) as follows ι

Spin Concentration

(1) Activated carbon 8.2 χ ΙΟ " ⁶

(2) carbon on alumina 3.1 x 10 "**

The inventive combination analyzer, which contains the above-described, low aoidity exhibiting material with the carbon dispersed thereon, is produced in the way that the carbon layer is in situ by the condensation of a suitable hydrocarbon coating material, for example, an olefinic hydrocarbon with 2 to 20 carbon atoms per molecule, for example styrene, butylene, propylene, Budatien, ι icosen and other Beschiokungsnuiterialien described above. The condensation for preparing einetweilige dee e is carbon but preferably carried out at a temperature in the range from 200 ⁰ C to 140o C or ⁰ 300 ⁰ C to 900 ⁰ C, particularly preferably from 400 ⁰ C to 800 ⁰ C.

009830/1879 ^BAD

■ Le has been found that the catalyst prepared as above, the beateht from the carrier material and from 0.1 to 30 wt. ^ Deposited on a support of carbon, or strapless used carbon (95 wt.% Kohltnatoff, wherein the Heat from -su & retoff, oxygen, sulfur, halides and the like it is also used for the dehydrogenation of normal dodecane to linear dodeoenes or also for the dehydrogenation of olefins to jJlolefins, for example of butylenes to iutadienes.

Other actions which are _{catalytically influenced by the erriridun v} ; agerB ^: i- »en carbon catalyst include the cyclizations proceeding with dehydrogenation, for example of paraffins (for example those with 6 to 8 carbon atoms), such as from heptane to toluene, and also from Cg paraffins to ethylbenzene and xylenes. ». If the carbon applied to a carrier of low acidity, for example a sodium-containing gamma-aluminum oxide, is used in conjunction with an acidic component, for example silica-aluminum oxide, this combination catalyst can be used for reforming, for example for reforming lighter petroleum fractions below. production of high octane ienzines, and for the conversion of methylcyclopentane into benzene; Furthermore, it can then also be used for isomerization, for example of n-octane in isooctane. Another possible use for the carbon catalyst, which has an acidic component, is the hydrocracking of gas oils with the formation of gasoline fractions in the presence of hydrogen.

FIR Verdun group of reactions n'iralich for Beformieren, Isomeriöieren and liydrokracken, finds a - ^r ATU

009830/1879 ~ - ~ -,

⁸⁴⁰

Iy sat or application, which is a mixture of two components, namely τοπ

a) 0.1 Lie 30 Gew.Jl (based on the total amount inws together ^ ": put catalyst") on carbon, dtr through the condensation of unsaturated hydrocarbons on one Carrier material of low acidity old with a cidity factor was boiled by not more than 2.0 atyre; and

b) a carrier material of high acidity with an aciditlita factor of nlcnt below 3.0.

Each of the components A) and b) can be present in a proportion of 10 to 90% by weight.

Bar described above · Catalyst is used for catalysis with a fixed catalyst bed, whereby a feed material is blown through the catalyst bed, which is kept at the desired temperature the temperature can be used "the erfiBdungsgea ^ .IEN catalysts are also f'ir use in .ysternen with Äirbelschichtreaktionen suitable _f in which the catalyst particles are suspended in a gas stream of heaktionspartner" as for example in a Kohlenwaeaeretoff-Beschickunjämsterialt or in "inea - Aastrom ge * ioer, ala diluent serving gases, such as nitrogen or water vapor. This process can be used in a reaction vessel in which standpipes are provided for moving the catalyst, which, if necessary, can be removed for generating

Paa Verfohren for the use of the invention Catalyst, which is produced by the separation of carbon

009830/1879 BAD original

the carrier material or the walls la inside the Reektionsgefäfles, consists in that one Schiokungsaeterial, do for example ethyl benzene, at a denydration temperature, for example from 400 ⁰ C to 800 ⁰ C, but preferably 450 ⁰ C to 70O ⁰ C, but the surface mentioned conducts and the reaction product is removed from the reaction vessel. A gas serving as a diluent, such as hydrogen, nitrogen, carbon dioxide, Wesaerdampf and the like, can be introduced in any desired proportion, for example from 0.5 to 30 parts of diluent per volume of the reacting substance.

The use of a diluent causes dehydration and in other processes such as the production of styrene from ethylbene sol, all of these are desirable. fell the conventional uasetsung is the diluent not only necessary, among other things, to supply the main amount of heat, but also by monitoring the weight of the reaction against the dilution effect a large volume of an inert gas moves namely the equilibrium in the sense that as a result of the Theraodynamiaohen Gesetsaasskelten a more favorable relationship the conversion of ethylbene into styrene is made possible. To push back the backlash requires dea conventional processes for styrene production are also used the highest possible temperatures.

The use of steam as well as other diluents, so for example nitrogen, carbon dioxide, carbon dioxide or methane, is therefore in the case of the above-described Reactions la regard to a shift in the balance in the sense that at a given tea temperature a higher proportion of converted material is obtained, likewise. • asserdaapf, however, has a specific property in this respect when a very large amount of heat is introduced into it,

009830/1879

which is necessary for the endothermic reactions; nooh harder weighs in when using. · t-seerdarapf for these reactions however, the advantage that this deactivates the Katalyeatora considerably rink t or even switched off, because the water vapor with the formed in the course of the reaction Coking residues reacts resulting in the inactivation of the catalyst counteracts.

In contrast to the above considerations are conventional Catalysts, such as activated synthetic iron ore, the inventive Kohlendtoffkatalydator, the example shows a greater selectivity in the dehydrogenation of ethylbenzene, so that et. side reactions are far less common comes, by which the toluene and benzene is produced, inferior. Accordingly, the styrene yields are also higher.

It was found that the carbon catalyst according to the invention has a greater selectivity typical for any conversion level than conventional catalysts have. The embodiment of the catalyst according to the invention is the combination in which a carbon which has been deposited by the condensation of otyrene is applied to an aluminum oxide of lower aoidity. When using this Kohlenatoff-Aluminiurnoxyd catalyst for the conversion of ethylbenzene into styrene may reach the ert of 96 $ dl · selectivity at 40 ^ strength conversion. In contrast to this, the use of a conventional hydrogenation agent, such as a potassium-activated, artificially prepared metal oxide, if the operation in a commercially used plant is switched off for conversion to 40%, provides an oil selectivity of only 91 *.

Appropriate for the various hydrocarbon conversions (For the invention it is often desirable to

009830/1879

lent thinning agents to be used, which are supplied to the katal, y sereaktionegefäfl with the Beeohickun ^ Bmiterial. Inert diluents, such as nitrogen, Atisserdauipf, carbon monoxide, carbon dioxide, or even flammable gas currents, including both Yasseratoff and Metfahn, can be found in the process according to the invention. I have found that in the processes described here for the modification of hydrocarbons, in which the catalyst is inactivated, for example due to the deposition of coking residues, a typical behavior of the inventive catalyst is that its deactivation rate is metyrical It is lower than the i-activation direction windi ^ 'speed _s which you get with knurled metal cantalvap.toren such as platinum or with aluminum oxide, as they are used in compositions, the comparable order. deliver action values

The Hydrocarbon Conversion Reactions According to the Invention can you guys using. water as a thinning agent be carried out, do feotgeutellt, Jns -asestoff at the same time counteracts the activation of the Katalyeatora.

That is preferred for carrying out the above reactions Thinners, especially for long periods of operation which no need for regenerating the fiatalyaetors exists, is, as could be established,. ^ eserd ^ mpf. Ouch was found to be the lowest when using steam Deactivation of the catalyst over long periods of time is caused · When examining the heating vessels removed catalyst mixtures it is evident that when carrying out the methods for modification described above of hydrocarbons which in the absence of *; i @ serdaepf formed · carbonaceous «mixture very heat-resistant is and a later removal bit help · from ■■ -ss & rdampf

009830/1871

resists. It was found that the presence of caustic vapor prevents the formation of large additional carbon residues which would otherwise deactivate the catalyst. The use of Anooerdampf as a diluent in the erfindungsgemäiton proceeded makes it in some cases nuch desirable assergasreaktion activators to enhance the effect of * use, in which the aas3erdamp £ with the newly deposited VerkokungsrUckstönden react and this is at least partially removed or the catalytic surface of cleans the additionally formed coking residue. Preferred activators in this context are the alkali metals, for example sodium, potassium, rubidium and lithium, which are used in proportions of 0.1 to 5% by weight of the total catalyst mixture. The presence of alkali metals also leads to the formation of more active carbon-containing dehydrogenation catalysts.

The invention is also embodied in it, ei esa one ^! Continuous heating is carried out over long periods of time, the level of the carbon content being kept essentially constant. This can be achieved even without supply of steam by a · controlling the temperature, so that the carbon initially formed, namely the SSIG high at a ratio m ^ temperature · deposited, for example, from 400 ⁰ C to 1400 ⁰ C, as an active catalyst for the under Reaction conditions of a lower temperature, for example at a temperature of 400 ⁰ C to 800 ⁰ C • rfollowing dehydrogenation acts.

Furthermore, control of the amount of the in the Resktionsgeffiß existing carbon ·· through the use by using steam as a diluent. In this case the presence of water vapor promotes the water reaction, which leads to the removal of the carbon. Accordingly exist Equilibrium relationships between the continuous

009830/1879

BATH ORIGINAL

Cutting of small amounts of fresh, catalytically active carbon and the opposite distance from Kohlenet of I, bo that the reaction for long periods of time without a «weeentlicne increase in the amount of available carbon · can be continued.

In a preferred embodiment of the invention, carbon is dispersed on a carrier material of low acidity. The Aeidit'it here dee used Tr igera lot of great v.ichti _t; it k *, as will be explained in untenatehenden. Although the orfindungsßeTnßen carrier flir usually aufwtiaen a lower Aoidität, known to many of the usual methods for determining dea Gäureaquivalcnte materials Triger-such can be beatimait "so have not all those Tri _fc 'he, having such low acidity, as proved satisfactory in the Kahmeη the invention. It has therefore arisen the need to use methods other than those generally customary for determining the aoidity in order to determine the characteristics of a lower acidity of the inventive carrier materials. In order to achieve this, the use of a model test has proven to be a satisfactory method for measuring acidity. Lie / nwenoung of model tests to determine the one k? Restrictions placed on analytical material is a generally accepted technique that has also been discussed in "Journal Of the American Comical Society, Vol. 82, pages 2471 and 2483 (1960). The acidity of the inventive materials is discussed herein in an" acidity factor ". reproduced. This AciditUtafaktor is determined by bringing the lrüger or daa Iritieraiaterial in a small ReaktlonBkeaiJibr i.it a Kohlenwiiäaerstoffmiachung into contact, the 92 wt. t n-rodecan and 8 Gew.?f n-alpha-dodecane in a mixture with . '. aaastoff in a molar proportion of a leii coal * .buerbtoffmachung to two parts ^ aseeretoff

009830/1879

contains. A temperature of 435 to 44O ⁰ C, an atmospheric pressure +, 0.141 kg / cm (+, 2 ρ ei) and a space velocity of the coal / fuel mixture of 4, 65 LHSV · maintained the reaction products from this model experiment are then passed through a Gaachromatographen whose Chromatographenuäule is filled with a substrate due suitable, the product mixture according to the respective boiling points and polarities disassemble »u, a fired for example with üuromoeorb VV ₁ with a Zuechlag Diatomaceous earth which has been treated with Carbowax 20 M and with smaller amounts of bilber nitrate and which is a suitable and preferred substrate. The percentage by weight of those materials in the reaction products which are eluted from the gas chromatograph before n-bodecan represents the acidity factor used here. The substances eluted from the gas chromatograph before n-odeoans are those components that boil lower than n- Dodeoan and which do not have such a polarity that they were preferentially retained by the adsorbent in comparison to n-dodeoan. If, according to the invention, the proportion by weight of these components of the reaction products eluted before n-dodeoan were "ei IO Öew.i *, then the acidity" factor dea affect "the question material would be expressed In the practice of the invention in dehydration, cyclization, which proceeds under dehydration, and in hydrogenation, the carrier materials or supports for the catalyst are presumably of low value, the aoid factor U generally not exceeding 2.0. Particularly · precautionary factors avoid dlt • rfindingegeaftSsB for equipment or carriers old with a lower weight an aoidal factor of not more than 1.0. The leetisemagsatthode used for the Asldlttttefaktsr is held to be krltlsom, since those trigtra material »odsr carrier, dl · lower than dl · duroh dl · obig ·« areneea beielohaetea Aeidltitsfactorea aab · », la lahaen elf« r Eraxflndlsun -IrUitt, stia eater Ata / drleruag verlauf · «··· Cy« ll »ler ·« aa4 IjrdrUr ··, w «alg« r * raa «h» ar «lad, eefera aloat utNiir

BAD ORiGiNAL

_o , IO

the carrier or the carrier-carbon mixture of another is subjected to preparation. This conditioning treatment can be in the form of an addition of more than 0.1 wt /. Alkalis or alkaline earths to the carrier or by other such Methods are used to thereby reduce the acidity factor to the desired value. Ingredients with high Acidity, however, are in connection with the inventions Carbon parts / components of low acidity suitable for creating a composite catalyst which is useful for reforming, isomerizing and hydrocracking. Such high acidity components have an acidity factor which is not less than 3.

nenngl-ion assumed in the oily discussion was to measure the acidity factor of the carrier while still no carbon is deposited on it, it is of course within the scope of the invention that the aoidity factor also of the finished product Catalyst on which carbon is deposited investigated can be. The determination of the aoidite factor of The finished catalytic converter is carried out using the method described above This model test and shows that · here as a result the implementation of the reactions described above in weaentliohen no day of attendance occurs

In addition to the internal fittings of the aluminum oxide and the other types of materials or carriers of the invention, the materials should preferably be classified in certain other categories and can be used in the case of the Krfin-type «Sit la · 11 <· ΜΐΒβη a · Oberflioae Ton less than 300 square meters art OrajM (geAean naoi Ur Bbt« M «thod · iurob A * a * r> U · * ve ·» tiak-itoff as from inuutiM iMMtt UBl plate »E« ohrle »« n Is "Journal · ί ta · laerlaan Okaei oal aooittyT» »ani iO ₉ leite J0% tt, 1 || β) · Torsufawel · · port iieee porter OWrflieaan v ·« waaigar al · tOO Qn « 4rata «t« r pr ·

Grama and especially preferably of less than 100 square millimeters per gram. Generally speaking, the inducible carrier materials have a macropore volume (pores that are larger than 100 areas) of at least 0.05 ml / g. Preferably, however, the most expedient acropore volume in the context of the cutting is at least 0.07 ml / g lift more than 100 nn ^ ötröm, whereby this .ert is related to the weight unit of the carrier material. The macropore volume is expressed as the Ακκβηΐ milliliters of those having a larger radius of 100 Angstroms per gram of the aluminum oxide. Another desirable criterion for the carrier material is that the micropore volume (ie the volume of those iores that are smaller, never 100 Angstroms) should not exceed 0.3 ml / g of the carrier and preferably not of 0.2 ml / g of the carrier ;; q11. The use of only those carriers which meet these restrictive requirements with regard to the acropore and micropore volume and the internal surface contributes significantly to the catalytic smell of the catalyst odor in terms of the equilibrium state of the carbon. The micropore volume is beatim ^ t according to the BT method described above. The macropure volume is determined with an Aminconinslow Hueckailberporosimeter, rodeil 5-7107, or with a corresponding mercury penetration device and represents the penetration of the inner volume at an overpressure of 0 to 562 kg / cm ² (0 to 8000 psig). A discussion of determining the acropore volume can be found in "Industrial and Engineering Chemistry", V. 17, 737 (1945).

. In a preferred .- ^ usf'lhrun AForm the rfindun.- 'is due IrHgermateriel or carrier f'Jr the erfindun _t' 8genr / IFLE Kf.t'ilyui. Tormischung from einenr Alurainiunoxyd. Here is

009830/187 9

a thermally stabilized aluminum oxide given the precaution * Thermal stability is understood to mean dose dae aluminum oxide Should withstand temperatures in the range of the intended reaction temperatures for 12 hours without this an essential linbuß · its inner surface eu suffer.

It has also been shown that, according to the invention Catalyst by adding compounds of alkali metals unu of the alkaline earth metals attached to the original TrH-gerbasisrauterial or are also known to be attached to the Tr'iger carbon combination, is improved "

The alkali metals which can be considered in the context of the invention include sodium, potassium, lithium, rubidium and cesium. The alkaline earth metals include, in particular, magnesium, calcium, barium, strontium and beryllium. Calculated as the free metals Liese ¹ Oteile, although, beieuielsv.eiae in the form of various compounds of the oxides or aluminates may be *

The amount of the alkali metal or alkaline earth metal present in the catalyst according to the invention is usually in the range of approximately 0.10 to 5% by weight, based on the total catalyst smell. It is generally preferred, however, that the veins of the alkali or alkaline earth metal present in the catalyst are in the range from approximately 0.20 to 3.0% by weight, occupying the entire catalyst mixture.

The alkali metal or alkaline earth metal can be applied to the aluminum oxide or to a liquid containing the mixture of iron and carbon by conventional methods such as gray infamous precipitation, soaking or impregnating and the like . are. Lei a special

009830/1879 ^ ^

8AD ORfGfWAL

the «expedient procedure for introducing the alkali metals or the alkaline earth metal in the carrier material is an alkali or alkaline earth metal salt in a suitable one Solvent, preferably if possible, in v'asder solved. The X-carrier deposited on the carbon can be or which can be free of carbon sequestrations, is then either completely immersed in the solution or becomes treated with such an amount of the solution that is just sufficient to make the desired amount of activator.

The following examples explain special ones Embodiments of the invention

Approximately 130 ml of cylindrical flakes 3.18 mm (1/8 inch) in diameter of a Grümraa aluminum oxide, also an inner surface (B, .T) of 74 m / g, a yiacropore volume (lores that are larger than 100 * n -9tr ^f 5m) of 0.12 ml / g and a micropore volume of about 0.20 ml / g (pores with a diameter of up to 100 Angstroms) and an acidity factor of 0.1 (as defined above) , are placed in a 61 cm (24 inch) long reaction chamber having an approximately 25.4 cm (10 inch) long & atalyaator space with a 2.54 om (1 inch) diameter, the carbon hydrogen feedstock described below 66.3 wt.! * # au "ethylbenzene, 32.1 wt. 1" aue styrene, 1,3 QTW. of toluene and about 0.1 wt. # au is "other hydrocarbons, is then at the same time as -ticketoff Diluent in a molar ratio of. Nitrogen su hydrocarbons such as 7.5 su 1 introduced into the reaction chamber. The temperature in the reaction chamber is kept close to 54O ⁰ C, and the pressure, which corresponds to substantially atmospheric pressure, is maintained in the reaction chamber. Until liquid hourly specs vslooity, LHSV, the hydrocarbon runs to 0.22 h " ^1. After a period of 30 hours the production of the complete

009830/1879 ^BAD

different carbon containing catalysis. atore ended. Honor dieeer period is kohlenatof: haltire oubatanz representing the active Ketelye & tor, on the Aluminiuxoxyd in a Men ge from about 10 percent carbon by # 'ondensation the unsaturated carbons * ■ deposited sser3toffe..

After a 30-hour catalytic converter build-up, the synthesis of styrenes from ethylbenzene is started. i other hydrocarbons, whereby the rozoritanttile for benzene, toluene and ütyrol respectively? part 0,: C5 G --- v ;. lie. Lie Keaktionsbedin Ungen ae Jtyrolsynthtsephr-ler in the hey triebsreiae üina the same as those of the · - t al./ "itorherutellung just dues hier'bei u aa Äthyibünzol-B ^ schiokun: .j: nf;. t'-rial to the - 'parts of the other hydrocarbon ^ toff-beaoniokun ^ smoterial occurs urid aercarbonatoff ^ eh; It des K _£ .tulya itors 10 to 15 (Jew.X concerns "^ t, whereby the aciUit'itef aktor vi-Mhr and the 66-St- ¹ Jn igen This is achieved by converting ethylbenzene into otyrol in a proportion of 34 to 23 wt 96% by weight of the total products.

For comparison purposes, the ^ is tyroleyntheee under the same Reaktionebedin ^ Ungen bit durchgeflihrt a catalyst containing 0 _f 4 Gew.il on Aluminiuinoxyd applied platinum. " The aluminum oxide carrier material is the same as that used for the carbon catalyst noted above. Here, a lower activity is observed, and ewar the I-latin catalyst amounts dad initial Ujba "and] ungsverhältnia In styrene f ^r Jr to 28 * with a 93 / strength selectivity la comparison tu a 34 ^ strength converting nit a 96 ^ ifen selectivity for the carbon analyzer

009830/1879

The carbon-aluminum oxide catalyst has an essential feature concentration of unpaired electrons, where 3 »1 x 10"

per carbon atom through the Klcktronenspinreeonana ^ enu. and the g-V.ert is 2.0027. In the opposite the latin aluminum oxide catalyst only shows this an insignificant concentration of unpaired electrons.

Will iroben this Kntalyaator in the consumed Form of the Klektronspinresonenzmeusung, eo is subjected feutjjeatellt, dnae dae ratio R of the opinion movements in a vacuum do the spin motions in air 590. This sample shows a relative synthetic activity in 1-butene dehydrogenation of 4.91 (Table I).

Execution 2

Approximately 130 si magnesium oxide i. 3.18 mo (1/8 inch) diameter bibs are placed in a 61 cm (2 # 4 inch) long reaction kitrojer which has an approximately 25.4 om (10 inch) long catalyst chamber with a 2.54 cm turcihraebaer (1 inch). The bibs, which consist of 98% by weight of KgO and 2% by weight of Al ₂ O, had an inner surface (W ^: T) of about 21 / g and a macropore volume (pores of more than 100% Angatron) of about 0.12 ml / g and a micropore volume (pores of less than lv; 0 Angetröa) of about 0.19 ml / g r'Uf. The reaction carried out in the example below is a cyclization which proceeds under dehydration and is preceded by a 1,2-vinylic acid. A 2,4,4-Trifsethylpi; r.ten-2-BeQChickur.jöm .-. Terifal Aird rleichzeitit "with; 3tickstoif zu XohU-nwf.6eer3toff like 0.9 to 1 introduced into the reection chamber -ieaktionsk-.a-.er wJrd maintained at about 43o C ⁰ in which:. .eaktion3kt: m-or v.ird a ^ jerk upright erlielten, corresponds to the substantially atmospheric derr Lruck Lie Fl'i.ü3i '. keitsraux _L i ·. lm;; viin..i _: 'keit (liquid hourly space velocity, LHw-Y) dee 2,4,4-Trin: eth _i / l _i t-nten-2 fcf; IMuJt oich to 0 , 50 h ~. The active catalyst is the one on the

009830/1879

"BAD OFBGlNAL

Surface dor ^ agaeeia during operation is a separated, carbonaceous substance due to the condensation of part of the olefinic charge material. This Kohlenetoff deposition takes place at the same time the old: NTET € htn a catalytic activity for the conversion of 2,4,4-Trimethylpeuten ~ 2 in p-xylene _t the IHST be shown schematically about 1 hour. Jiach ending a 48-stan-ended farms Travel betriigt the carbon content of the catalyst about 6 ÖE *.? F _f the environmental "-andlun ^ p-2ylol amounts to 2.2 wt. F and the! /! Narrow proportion of the p-Xylola on the xylene fraction of the reaction product is greater than 99 *

Yird this Auaf ^? lhrungebeiepiel repeated geranterial using i.ta-AluminiuBioxyd as fr ^, (the inner surface of this Aluuiniuaoxyds · belauft sichauf 200 ■ / g, the Porenvoluaen the pores below 100 at _t; ströai beelffert to 0.25 Al / g of us Acidity factor to about 0.2), a similar result is obtained.

The carbon combination catalyst in which either Magnesia or aluminum oxide are used as the basic substance finds, is also an effective catalyst for the cyclization proceeding with dehydrogenation, which without Isoaerisatlon takes place on the carbon framework. So he promotes s. B. at about 530 C the conversion of n-heptane into toluene.

130 ml cylindrical platelets from Eta-Aluuaoiyd-Tr ^ geriBsterial old a diameter of 3 18 as {1/3 inch), which has an inner surface (Bi-T) of 94 » ² / gt« in macropore volumes of about 0.11 al / g and a micropore volume of 0.30 al / g of pores that are smaller than 100 an ^ etröa, so ^ ie an acidity factor (as defined above) of 0.1.

009830 / 1-879

are placed in a 61 cm (24 inch) long heating chamber that has a catalyst space approximately 25 »4 cm (10 inches) long and 2.54 om (1 inch) in diameter. A carbon dioxide chemical material consisting of 66.3% by weight from ethylbenzene, 32.1% by weight from styrene, 1.3% by weight from toluene, 0.2% by weight from benzene and at 0.1% by weight of other hydrocarbons is then introduced into the reaction chamber at the same time as nitrogen, which serves as a diluent, in a proportion of nitrogen and carbon dioxide. The temperature in the Reaktionskaairaer is maintained close to 540 ⁰ C. A pressure which essentially corresponds to atmospheric pressure is maintained in the reaction chamber. i) The liquid hourly spaoe velocity (LIISV) of the hydrocarbons amounts to 0.22 hours. After a 30-hour business trip, the production of the deposited carbon-containing catalyst is complete. During this period of time, carbonaceous substance, which is the active catalyst, is deposited on the aluminum oxide in a proportion of about 10% by weight of carbon.

After a 30 hour period of catalyst preparation the synthesis of styrene from atirolbenzene is initiated. The ethylbene sol feed contains 98.2% by weight ethylbeneol and 1.8 wt. ^ of other hydrocarbons, where the percentages of benzene, toluene, and styrene are each 0.005% by weight. The conditions of the styrene synthesis the operating cycle oind the same as that of the catalyst production, only that in this case the ethylbenzene feed material in place of the other coal feed materials occurs and the carbon content of the catalyst during the 66-hour company trip · zur ötyrol- • yntheae 10 to 15% by weight. During this period the conversion ratio of ethylbenzene to styrene is in the range from 34 to 23 Gew.Ji and the selectivity of the styrene amounts to 96% by weight of the total products

009830/1879. ,. _t

BAD OFHGJNAL

If this embodiment is repeated using an activator, namely 1 $ copper (calculated as ale ... metal), which was obtained from a copper nitrate deposited on the aluminum oxide, the properties with regard to the inner surface and volume remain of the small i ores essentially unchanged. The efficiency for the hydration also remains essentially unchanged.

Execution example A

.bin K <, tal,> uBtor becomes as in execution run ^ abeie. As described in Section 3, the time span of the operational journey for the production of the Ktjtslysatore is 19 hours. At the end of this., -; If the catalytic converter fails, it has a carbon content of about 10%. When the weight division of the catalyst has been completed, a ethylbenzene-carbonate material is formed which consists of 9B.2% by weight of ethylbenzene and 1% by weight of other hydrocarbons, the percentages for benzene, toluene and jtyrene are in each case 0.005 wt. ^, ^ on the other hand with. -.Bserdauif.f, which serves as an innuncitary agent, is introduced into the Heaktlonska.er in a molar ratio of water to hydrocarbons such as 8.5 to 1. The temperature in the reaction chamber is ^{kept close to 57O 0} C, the pressure prevailing, four substantially corresponding to the atmospheric pressure. .The FIU & si ^ keitsrausigeijci.win ägkeit (liquid hourly space velocity, LKoV) of Athylbonzola amounts to 0.12 h ^"*; ihrend the 25-atindigen period of oynthesebetriebareiae amounts to the SW / andlun ^ averhHltnis of thylbenzol in ttyrol on average 43 The selectivity of the styrenes extends to 91% by weight of the total reaction products. In this operation, the final carbon content of the catalyst combined was 11.5 Ci

• Ird this Ausf'lhrunjsbi'ia ^ '- el using Titanium oxide as carrier material and of Hexen-1 as foal

009830/1879

source f "repeated for the I ohlenatoff ebectitidung so" 3hrt the rzeugung of styrene ouch Atfaylbensol au a ^ similar; t.eaultat as the obenbesehriefoeiien In dieaer modified for "does constitute a catalyst support Acidit'itaf aktor of 0.7, a. inside- T9 surface τοπ 10 a / g, m ^: ihrend iae Yoluaen derjtmißen .iren, which is kltinar aind than 100 an ^ striSa, about 0.15 itl / g.

If iaa ^ steam is advertised as V ^ rtHjnnunjü-iiittel, a "continuous" smear of carbon oxide is provided. ttenn _(lvicli the ndaenge of carbon Aich not iteaentlich changed, but <3 Xistalysr.tor iat eelbetregiberierend, ao that long Betriel airhrten duroh can _t ief'ihrt without the catalyst aas the EeaktionslAiner remove m'ia s..

A Katalyeator as la AUEF ü _ran: Made> bi-iapiel 3, only daaa case the carrier material ouch Garnsia-Aluainiumoxyd by an addition of 2 ^J Hatrium that ouch of a steep old sodium nitrate hot n CHF oil -enüein Kai "inier" η! originates, modified itird. The charring "irdl · - · ie la Äuaf! Ilirun £; sbeiepial 3 carried out, only that the division of the kohlenatoffhal i -en Ki.talyaatora is completed in the course of 6 hours * Ti" Jynthea "des c'tyrols aud ethylbenxol is introduced after the six-hour preparation period, while a change is made between tiiylbenzol as i: eachikkun ^ ssiaterial and .isaerd ^ ajf fcla Yerd'dnnunjsinittel. Las volvorhSltnia of i'aaaerdampf «u ithylbenaol amounts to 7 _f 5» u 1 · 5Ie Aaeperatur entered 54O ° C and the water resistance resistance (LHSV) amounts to 0.24 h "* ¹ , The conversion to styrene aacht from 36.5 percent, with selectivity "ratreckt ill di · FlisBigkeitarau." 96.5 f - gcschKi & äiglceit (LHS ¥) modified h in such a of 0.12, the conv-snilung done in Styrene su 41 * ■ with its selectivity of 96 i »* rs it is made sure that the

830/1879 t - '

BATH ORIGINAL

Deactivation does not apply when using ftaeeerdanpf All diluents are far less let than btl dtr use of nitrogen ale diluents in combination old dt « same catalyst and under the same reaction conditions.

Subjects Ban samples of this catalyst to "5.2% by weight of carbon." contains, in the used fora of an electron spin resonance aspiration, a ratio R of the spin motions in vacuo to the spin motions in air is found in 1453. These Sample shows a relative catalytic effect in the dehydrogenation of butene-1 Activity at 10.1 (Table I).

Execution game 6

The catalyst is prepared as in embodiment 3, but butene-1 serves as the source of the deposited carbon, which is obtained in an amount of 12% by weight of the geeaate mixture with 3aaaa-aluminum oxide. The preparation of the catalyst is completed, an ethylbenzene-Besohikkungsaaterial, of 93.2 wt. I »Athylbensol and is 1.8 wt. ^ Contains other hydrocarbons, wherein the Preosentanteile for benzene, toluene and styrene respectively to 0.005 wt.? * amount, simultaneously with nitrogen, which serves as a diluent, in a MolverhUtnia τοη nitrogen ku hydrocarbons such as 7.5 su 1 introduced into the reaction chamber. The temperature in the reaction chamber is kept at about 54O ⁰ C, the iruok generally being the atmospheric one. The liquid hourly apaoe velocity (LHSV) of the ethylbenzola amounts to 0.11 h. During a 28-stUndigen 3ynthesebetriebereise is the Um> andlun ^ everhaltnie τοη Äthylbenaol in styrene averaged / 33 wt. + And the styrene selectivity extends calibrated to 95 wt. * Of Gesaat- ■ close the reaction products.

/ is this implementation report using /; * is added sodium nitrate sodium herr'lhrenden an alpha-aluminas as a support, to which 1 wt. 1 is repeated, with the inner surface about 1 ■ / g, the pore volume of the pores below 100

009830 / 1-879

Angstrom 0.10 1 / g and the aoidality factor about 0.2 1, so it is obtained one has an approximately · enhanced selectivity «

Execution area 7

Ea is a catalyst in is Heise prepared dna "one at a aamaa-Aluminiurnoxyd» it a Aoiditätafaktor O ₉ I by Einan contact Bit - ** skinning 1 at 54O ⁰ C under Anwandung a Gaaraumgeschwindigkeit (gaa space velocity) of 7 minutes "examined for a suitability for the butadiene preparation. Since the baohlokunga material consists of butene-1, which is diluted by 3 volumes of nitrogen. As a result, a conversion of 8.2% into butadiene with a selectivity of 80% is obtained.

If the material to be considered is a laoaaylen old with a purity of 98 i-> and the same catalyst and the same reaction conditions are used in an * -endunt; brought, ao one obtains a 10 ige conversion in isoprene old with a selectivity of 81 %.

A catalyst is prepared as in Example 3, except that the reaction time for the preparation of the catalyst is 19 hours. At the end of this period the catalyst has a carbon content of about 10% by weight. Let the processing of the catalyst end, ao an n-dodeoan.be echickungsamaterial »the 99t5 öew. # n-dodeoan, 0.67 wt Nitrogen, which serves as a diluent, is introduced into the reaction chamber in a molar ratio of nitrogen and carbon dioxide as low as 4.8 su 1. The temperature in the reaction chamber is maintained at about 515 ° C., the pressure essentially corresponding to atmospheric pressure. The liquid hourly apace velocity (LHST) daa n-Dadecans amounts to 0.67 h " ^1. During a 52-hour synthesis reaction aaeitapanna an average enveloping ratio of

♦. which lasts 27 hours, a carbon deposition

w ^ k

takes. This catalyst is at 540 0 - * ~ ~ *

009830/1879 BAD OB.G.NAL

n-Dodecane in n-Dodeoene τοη 9 Oe *. £ obtained, and the selectivity for the development of τοη n-dodeoenes is 50
A similar result is obtained, based on the quantity of the reaction products, when the coating material consists of a mixture of normal alkanes with 10 to 15 carbon dioxide per oil.

009830/1879

If this is not possible, using an alpha aluminum oxide with an inner surface area of about 1.0a ² / g, a lore volume of the pores below 100 Angstroms of 0.05 ml / g and an acidity factor τοη about 0.2 repeated as carrier material, ao a similar result will be achieved

The two types of aluminum oxide with carbon, show kataytische Hydrokrackwirkun ^ s at higher temperatures Ruch, ao beiapielaweiee at 600 ⁰ C, falling to a gas oil ait an average composition of C ₂ ^ 'ogether with "asaeratoff in the ratio of Vasserstoff au Rohlenwasserstoff as 10 employing su 1, wherein a wild heaktlonaprodukt obtained that predominantly in Beneinbereioh boiling (nndpunkt 204.5 ⁰ C, corresponding to 400 ⁰ F).

AuafUfarunÄSbeisplel 9

A catalyst is produced in AuafUhrun _o sbelspiel 3. This consisting of carbon and (iBaaa-Aiumlniumoxyd material is mixed with an equal Qewichtsmenge of Silioa-alumina Pertikeln the same Sröfle that about 12 ^{Qewichtsproxent;} mechanical laoht contain illca Kusaamenge- ■ This oemiaoh * · catalyst comprising about 5 Gewiohtsproeent carbon. contains, is combined in a reforming process with a mixture of methyloyolopentane initiated. the temperature in the wild heaktionskammer maintained at about 54O ⁰ C, a pressure of about 49.2 kg / cm ² is (700 psi) in use. the FllieaigkeitsraumgeschKindigkeit (liquid hourly apace velocity, LHßV) of Methylcyolopentan belauft to euf J, 5 h " ^1. After a 100-

009830/1879 ^

BATH ORIGINAL

hour; reaction time let the average conversion ratio of ttethylcyclopentnn in benzene 50 (iewiohtuprozent with a selectivity of Θ0 percent.

If the above catalysis gate is used under similar heating conditions to isomerize n-octane to isooctane, then comparable conversion and selectivity values are obtained. The obi _b e kohlenstoffhaite Kombinetionskatalyeator also shows kfitalytibche fiydrokraokwirkungen when zuaammen a nniihtheniachca Geaöl with an average of C ₂ Molekillgrö3e Q with <aaaeretoff in a molar ratio of ..asserstoffe to Kohlenwasaerstoff 10 uses to 1, wherein a lower molecular weight icaktions ^ xodukt occurs, which boils in the benign area (indi-point 204.5 ⁰ G, corresponding to 4CO ⁰ F).

Execution example 10

A catalyst is produced as in Example 3, except that the duration of the operating journey for the production of the catalyst is 20 hours.At the end of this period, the carbon content of the catalyst is about 10%. When the preparation of the catalyst has ended, an n-butnut-acidic material is added which contains 98.94 percent by weight n-lithium, 0.97 percent by weight 2-ethylpropane unsi ^, about 3 percent by weight of other hydrocarbons, _c. At the same time with nitrogen, i.e. ^ r · - la VeidünnunftSmittel serves, in a "Aolverhaltr.ia from nitrogen to hydrocarbons ftie 2 to 1 introduced into the reaction chamber. The reaper« door in the ι eaktionakaomer is ^{kept at about 54O 0} C, whereby essentially '; an atmospheric pressure foresees. i-ie i - aiaum ^ eochwindi ^ keit (. ^ as hourly space velooity, J ^! '"7) de3 η-butane amounts to π i au: 36 h. i-; ch a 16-atün-

009830/18 * 7 9

long tent span of the 3ynthe8ereaktlonsasi | I counted there Uauandlun ^ arerhaltnis τοη n-Butanef tuf 8.6 weight percent and that for conversion to 1,3-butadiene to 0.8 Weight percent and farner extended aioh dia üelectiTität for the summa on the spontaneous generation of n-butanane and 1,3-butadians geriohteten processes to 73 percent by weight of the ge entire reaction products.

this execution example. using τοη Titanium dioxide as a carrier material and τοη hexene-1 as carbon source for carbon deposition repeated »ao a similar result will be obtained. Modified in servant JPorm, the catalyst has an aciditaxa factor of 0.3 »one inner surface τοη 10a / $, while the volume of those Forums smaller than 100 Angatrita is about 0.13 ml / g.

In a further, modified form, aaaerdampf in a molar ratio of 5 * u 1 to the sole dung amattrial is used as a diluent, when using steam as a diluent, a continuous formation of carbon oxide is observed, and the amount of carbon is not essential changes, the .Catalyst is selbatregenerierend, so long DAT operations rides can be carried out to remove from the talyaator Keaktionskanuaer without the K.

Version .sbela ciel 11

A catalyst is produced as in Example 3, only this is the reaction time for the production of the catalyst is 20 hours. At the end of this period the carbon content of the catalyst is about

009830/1879 bathroom

10 percent. When the preparation of the catalyst has ended, a propane-desiccant material containing 99.2 percent by weight of propane, 0.6 percent by weight of ethane and 0.2 percent by weight of methane is introduced into the reaction chamber, no diluent being used. The temple nature in the heaktionskamaer is kept at about 570 ⁰ C and the iruuk corresponds essentially to the atmospheric pressure. The gas hourly apaoe velocity (OrHW) of the gaseous eechickun.j, emateriala amounts to 40 h " ^1. During the 20-hour synthesis reaction period, the conversion of propane to propylene averaged 15.6 non-percent and the salivity The reaction directed to the formation of propylene extends to 73 percent by weight of the Isaataen ^ e of the heaktiona products.

If this embodiment is repeated with the addition of a granular, porous ulicium carbide as the carrier material, which contains 1 percent potassium (from Kaliu-iini rat) and is repeated from uensol as the carbon source for the carbon separation, a similar result is obtained. In this modified form, the catalyst has an acidity factor of 0.1, an internal surface area of 0.5 _{· / o} · while the volume of those pores which are smaller than 19µ angstroms is about 0.03 ml / g.

In a further modified #ora A than koaiat ait a i.einheitsgrad by 93 percent than the above, carbon and Aluoiniuaoxyd containing catalyst in use, wherein the dehydrogenation at 0OC ⁰ C under _r ü generation of ethylene is efiihrt luxch ^ and wherein 15 percent conversion to ethylene is achieved with a selectivity of 85 percent.

009 8 30/1879

Attsftlhrumtabelsplel ΛΖ

A catalyst is set up as in the embodiment 3. Since the hydrogenation of a catalyst consisting, among other things, of carbon and a catalyst of low acidity, can be influenced most effectively by the presence of an activator, the composite catalyst generally has a proportion of. 1 to <? . -weight sprouts of a noble metal, such as beisj-iela, eise ilotin, palladium, hubidium O'ier I.heniuu nufj in Jen ei finiun, β ^ βΐηίΐίίβη embodiment forms are hlexl'Ur 0.5 percent weight percent 1 latin in use, the alp the Krtalyaatorbeimiechunö is designated to graze, the carbon dioxide 'Muainiumoxyd- iachunö is first divided in gea. ° "ie vvirJ« cools and the t eak ti one I ram er -taken, what the 'Uq lenatofI- / luainiumoxyd -'ischun _t i with i If! Tin in r ^l or: n of il tindiaminodinitrit duro-soaked

A mixture with active toxicity v.iid at 1JU ⁰ C 0etr0c.net and gut at 3Oj ⁰ C in a nnsaersloffataosphäiβ ktilBin.ieit. -er 1 latiti ^ ehelt was 0.5 percent. Lieoer Ketalya tor proves to be an eact . η au3 with »aeaeratoff verdUnntecD benzene, where that? Y "olverh Itni3 the <a & eeratofis sum - Enzol 1> to 1 oeträ_t, kei 100 C with a / 'Jüsoi; - keitsraumaeoohwindigkeit (rate UUV) of 1 _f J h in a i.eaktionskammer a ^ oepeiat wild, never; -ehi confused hydrogenation catalyst .. - i «ii'mi.andlunt of: 5βη« ο1 in cyclohexone to 93 % oei an eleitivltit of ^ ..j rro «i; nt.

iin further ilement, Ua vatalyantoi available Ain mark in the •, int cLwefel. ..the presence of chAefel, - at he now in. "01 in a jondered Koaponentti wit- bei.'i ieleweise Sch ^.. -felwaast-iatoff, i'hiophen," ethj laieicfiptan eier der: .ο · ΐ. ο1θό ^ η to ^ e.jc-tsit, 'or be he in

009830/1879. * ■ · - -.

BAD ORJGJN / ", '.

-44 - 15930/12

the carbon-forming üesohiokun »material present, is for example for the dehydrogenation of saturated hydrocarbons to monoäthyleniach unsaturated products he wishes. Saturated hydrocarbons such as paraffins are usually considered by all coming substances of dehydration the greatest difficulty contrary to that, however, it has been determined that sulphurous Carbon is an exceptionally strong one ■ irk: have the capacity for the dehydration of each affine.

They are a lot more active in the dehydrogenation of a paraffin than similar catalysts, which contain little or no content in the carbon phase of the catalyst, a very general property. For example, sulfur-containing catalysts show a greater activity in the dehydrogenation of η-butane, nJ) odecane and cyclohexane. In addition, these sulfur-containing micro-analyzers also show a greater selectivity with regard to the formation of mono-olefins compared to non-sulfur-containing micro-catalysts. 3o is greater, for example, in the dehydrogenation of η-butane, and even in the dehydrogenation of higher n-Iaiaffine, such as n-dodecane, at achwefdhalti _J en catalysts Ue on the formation of mono-directional selectivity, i-io formation of diolefins and unsaturated higher liodukten occurs DEM ^ _e; , enUber back. It follows that the presence of sulfur in the range from u, 1 to 10), ichtsprosent, calculates ttla / iUivaletit elementary sulfur, arises for those catalysts which are to be used for the dehydration of saturated olelcules . Such catalysts are not only usable for the dehydrogenation of Cpbis Ο _{? Η} -Ρβΐaffins, but can also be used for the

00983 p / 18 Z9

Dehydration of saturated carbon-carbon-Ji into functional group-containing molecules, such as those present, for example, in esters, nitriles or chloro groups, are used. ^; For example, iropionitrile can be converted into acrylonitrile and ethylohloride into vinyl chloride. Me sulfur-containing Kohlenstofi'misohungen for the dehydrogenation sown-saturated Kohlenatof ι -Kohlena toi'f-iiindun ^ s in laraffinen or other or. ^ Niachen molecules may be included, which either contain or i'rägermaterlalien eini strapless. Chkatalysatoren in Juei ^ In the latter case, ttt-.r Ui --chkatalyaator in = 'er contains the main carbon and a lesser amount of fäfn ^ e Uchv / efel. There are "l.jtalloxyJe ala -rä ^ ermeterialien in the awe-containing fire catalysts, ao eo is not necessary, ao it is a matter of milling cutters .it lower! Acidity is all about. In fact, it seems to be in a hurry to have tracers with a high acidity as well as a high acidity for sulfur-containing tracers.

BATH ORIGINAL 009830/1879

Claims (21)

1 · Verf-ι, Μβη for the chemical modification of such carbons, iiö .vue of the ".ua the paraffins, the yonoolefins and the alkylnroiaitiec: en Koaleuwaa.eretoffen b-ja ts-.enden) group auacew'ihlt elnd, 1 idaroh ^ ö.iermzeiohnet that the carbon fuels are sufficient to u: nh "3ner unjjes vttl ^ te excrement l'j.j-aSütii'Btoffvi : i ι >? r3eugen, with ninen iatulyrii'tor in. er iiirun _fc ' -yhr .o.it erio: _lf dor van «..1 uin y .. ) e-« vicntüproaent einu iuro .. > \ Yo. ! Ion e.-isa.ion unj-'ü itti-.ter Io lon · aaHcri: tof fe ibgeuoni'jJä.ieu. ^: ohloiiEtoffs, bea-o ^ en iuf Jen 2üs-iGnioniöaetzti. Catalyst, e; »tnilt, .ooei Jieaor Uo » I · ¹ fabric luf ei. poritje ^ Jr * _; ;; r tteri »i lower cLiitit u.it einu. "iOiaititEfvticDor ve. nioht " ioor 2 * ~ : -. uf ^r jür: ioht i; t, vobei the zae t.nxan e sat catalyst a iI;. '3rsio ^ .- / rad of Kohleiiötoffa .on ■ = üiöt "Get a- ^ ert Ii VO" üoer b fir the V-jrhiLltniB the le "'tr; e.:, ■ / ■ i.-röBOn-jnz, dia als üe üezlehung ζ i.chen iHr ".a. _t ,; l aor. lnbe ^ eguug «n in the VuKkuai and the Aii ^ ui'il ier, in ^ eAe ^ ungen ir! Lui't formaliext iot, corresponds to 2 · Verfahret, zua cnö ^ iyonen odifikijren aolci ^ r: ioiili; .- '. VuecerBtoffe, the auü der tu de ^ raraffinen, the ioaioiefinen uud the aikylaromatic iionl iuwut-seratoffen ait Ί bia 20 Koi.lenatDffutomen i :. der uilcylicette: j.; etei. * iide; i Jr.ippe aut'_e - '«iihlt oin ·" !, thereby ^ eksr.nzvlahwt, d.rea' Jie «'. Kohl ^ι · .λ388 · ϊγ-ötoffe with an j: n; -jratur, oai eiiit .. ·. Lruck u..d in a Ko.it.-ktzeitepanne, iie hinreior.en, among other things h.har \ iu _L ais itti ^ - te kohluiiaasorstoff, ix.it ^ inou 'latalya ^ tor be brought into contact, which of ~ .1 bie 3 ^ ie -'; iontpro «if; nt a through the condi It contains deposited carbons, related to the added catalyst, but with all carbon monoxide on a porous iluminium oxide material of eraiaterial lower aoidity with a 009830/1879 Aoidity factor of not over 2.0 is applied. 3. Verf liren naoh claim 1, daduron characterized that the charcoal raw material Xthylbenzene is anhydrated to styrene. 4. The method according to Claim 1, characterized in that the hydrocarbon feedstock η-butane is dehydrogenated to n-butylenes. 5. The method according to Claim 1, characterized in that the hydrocarbon inventory Propane is that is dehydrogenated to propylene. 6. The method according to claim 1, characterized in that the hydrocarbon loading criterial Butylenes pind, which are dehydrated to butadiene. 7. The method according to Anusruch 1, characterized in that it sioh with your - <us Kohienwass Tstoff existing Beachiokungsmaterial is n-alkanes of the series C10 to C15, which are dehydrogenated _{to linear olefins of the series C 1} ^ to C _{1 C.} 8. The method naoh claim 1, daiuroh characterized in that the hydrocarbon deeohiokungematerial Isoamylene is dehydrated to isoprene. 9. Verfuhren according to claim 1, characterized in that the hydrocarbon feedstock Ethane is dehydrated to ethylene. 10. Process for the dehydrogenating cyolization of aolonic hydrocarbons, selected from the group consisting of paraffins and olefins having up to 20 carbon atoms per molecule are characterized by the fact that these hydrocarbon 009830/1879 . ^ BATH ORIGINAL substances at an elevated temperature, pressure, and contact time sufficient to become aromatic Generate hydrocarbons in contact with a catalyst be brought from 0.1 to 30 percent by weight of a by the condensation of unsaturated hydrocarbons Deposited carbon, based on the composite catalyst, contains, this carbon on a porous carrier material of low aoidity with an aoidity factor yon is not applied over 2 * 0. 11, method according to claim 10, characterized in that daee the hydrocarbon pollutant is n-heptane, which is dehydrogenated to toluene. 12. The method according to claim 10, characterized daduroh, daee the hydrocarbon pollution Diisobutylene is dehydrogenated to p-xylene 13. The method according to claim 10, characterized in that the hydrocarbon-based coating material n-0otane is dehydrogenating to ethylbenzene and xetolene is oyolized. 14. Process for refining such hydrocarbons, which are selected from the group consisting of the alkyl-substituted cycloparaffins and olefins, daduroh marked, that dieεβ hydrocarbons at an increased Temperature, at a pressure and contact time sufficient to produce aromatic hydrocarbons, be brought into contact with a catalyst which is a mixture of the two components a) ron 0.1 to 30 percent by weight o through the condensation of unsaturated hydrocarbons on a carrier material of low acidity with an aoidity factor 009830 / 18-79 of not more than 2.0 deposited carbons »based on the composite catalyst, and b) a carrier material of high aoidity with an aoidity factor of not below 3.0 contains. 15. Process for isoerating such hydrocarbons, which are selected from the group comprising the paraffins, characterized in that these hydrocarbons in a elevated temperature, at a druok and in a contact period, which are sufficient to have branch points. de generating hydrocarbons with a catalyst in Brought into contact with a mixture of the two components a) from 0.1 to 30 percent by weight of one by the condensation unsaturated hydrocarbons on a carrier material lower aoidity with an aoidity factor of not more than 2.0 carbon deposited on the composite catalyst, and b) a carrier material of high acidity with an aoidity s factor of not less than 3.0 contains. 16. Process for the hydrogenation cracking of such hydrocarbons, selected from the group consisting of paraffins and olefins, characterized in that diene Hydrocarbons in association with hydrogen at an elevated temperature, pressure and contact period, which are sufficient to produce hydrocarbons that boil in the gasoline boiling range, with a catalyst in BATH ORIGINAL 009830/1879 be stirred, a mixture of the two components a) from 0.1 to 30 percent by weight of one by the condensation of unsaturated hydrocarbons on a carrier material of low acidity with an acidity factor of not more than 2 0 deposited carbon, based on the composite catalyst, and b) a carrier material of high acidity with an aoidity factor of not below 3.0 removes. 17. Process for the hydrogenation of such hydrocarbons which selected from the group consisting of olefins and aromatic hydrocarbons, characterized in that that these hydrocarbons in verse with at an elevated temperature, at a pressure and in a contact period, which are sufficient to make more saturated hydrocarbons to produce, are brought into contact with a catalyst that contains 0.1 to 2 percent by weight of a noble metal and from 0.1 to 30 percent by weight of one by the condensation carbon deposited of unsaturated hydrocarbons, based on the composite catalysis gate Contains, this carbon on a porous carrier material of low acidity with an acidity factor of not over 2.0 is applied. 18. Catalyst, characterized by a content of 0.1 to 30 percent by weight of a porous irä ^ ermaterial deposited carbon, based on the composite catalyst, this carbon through the condensation unsaturated hydrocarbons is boiled off. 009830/1879 19 · Catalyst, characterized by a content of 0.1 up to 30 percent by weight carbon, based on the composite catalyst, this carbon being produced by the condensation of unsaturated hydrocarbons on a porous carrier material of low acidity with an acidity factor of not deposited above 2.0. 20 «catalyst, marked with a content of 0.1 up to 30% by weight of a3; i on a porous carrier material deposited carbon based on the composite catalyst, wherein Gießer carbon duroh the condensation unsaturated hydrocarbons on a porous tracer material lower aoidity with an aoidity factor of not more than 2.0 is deposited, the composite catalyst having a degree of carbon de-dispersion, the one R value of aoer 5 for the ratio of the electron spin resonances, that as the relation between the number of Spin motions in a vacuum is formulated as the number of spin motions in air. 21. Process for the production of a catalyst which contains a porous iriauterial, on which a form of carbon is deposited, for which a high concentration of unpaired electrons is typical, because this carrier material is characterized by a temperature of 2JO ⁰ C to 14UO ⁰ C brought into contact with an unsaturated carbon dioxide and this unsaturated hydrocarbon is condensed to carbon, the carrier material having a cidity factor of not more than 2 ° C and the composite catalyst having an dispersion factor des Konlenatoffs, which gives an il -. * ert of over 5 for the ratio of the electron spin resonance, since the relation between the number of dej? apin movements in a vacuum to the number of 3-inoevegungen is formulated in air. 009830/1879